Related Pergamon Te of Interusl

Tetrehedron Organic Chernitn/ Ser:
CARRUTHERS: Cyclo==dd'on Reactions in Org=mlc SyntheeB
DEROME" Modem NMR Technique== f r Chemistry Reeeamh
DESLONGCHAMPS. Stereoelectroniў Effecte in Organio Chernitry
GAWLEY: A,/mmetriў Synthesis °
PAULMIER: Selenium Reagent= & Int=rrned'rates in Organic Synthesis
PERLMU'FrER: Conjugate Addition Reactions in Organic Sytthea
$1MPKINS: Sulphonea in Organic Synthesis
WLLIAMS: Synthesis of Optically Active Alpha-Amino Acld
WONG: Enzymes in Synthetic Organic Chemistry

BIOORGANIC & MEDICINAL CHEMISTRY
BIOORGANIC & MEDICINAL CHEMISTRY LETTERS
JOURNAL OF PHARMACEUTICAL AND BIOMEDICAL ANALYSIS
TETRAHEDRON
TETRAHEDRON: ASYMMETRY
TETRAHEDRON LE-I'TERS

Fu# details of a# Elsevier Science publicatonsffree specimen copy of any E/sewer Science
journal are avallab/e on request from your nearest E/sewer Science office

• In Preparation

Organic Syntheses
Based on
Name Reactions
and
Unnamed Reactions

Ao HASSNER
Department of Chermstry,
Bar.lien Universy, Israel
and
C. STUMER
Teva Pharmaceutical Industries,
Netanya, Israel

PERGAMON




UK.
U s.
JPAN

CONTENTS

Foreword
ReacUons (arranged alphabetically)
Names Index
Reagents Index
Rections Index
Functional Group Transformations Index

vi
1
439
447
451
453

ISBN 0 08 O4028O I Handcover
ISBN 0 08 040279 8 Flexўover

Pnnted ,n Great B.taln by BPC Wheaton Ltd Exeter




Non nova sed nove

FOREWORD

And these are the names...

The above are the opening words of Exodus, the second book of the
Petateuch. Already in ancient times, names were important in association
with events. As orgamc chemistry developed during the 20th century,
researchers started associating synthetically useful reactions with the
names of discoverers or developers of these reactions. In many cases
such names serve merely as a mnemonic, to remember a reaction more
easily; there are few chemistry undergraduates who do not know what the
FriedeI-Craffs reaction is.
In recent years there has been a proliferation of new reactions and
reagents that have been so useful in organic synthesis that often people
refer to them by name. Many of these are stereoselective or regioselective
methods. While the expert may know exactly what the Makosza vicarious
nucleophilic substitution, or the Meyers asymmetric synthesis refers to,
many students as well as researchers would appreciate guidance
regarding such "Name Reactions'.
It is in this context that we perceived the necessity to incorporate the
older name reactions with some newer name reactions or "unnamed
reactions", that are often associated with a name but for which details,
references and expenmental details are not at everyone's fingertips. This
was our inspiration for the current monograph "Organic Syntheses based
on Name Reactions and Unnamed Reactions".
In particular we thought it would be useful to include cross-references
of functional group transformations and an experimental procedure, so that
the reader will be able to evaluate the reaction conditions at a glance; for
instance s this reaction carried out at room temperature or at 200"C? For
1 h or 5 days? Are special catalysts required? How s the reaction worked
up, what yield can be expected?
The choice of which reactions to include is not an easy one. First
there are the well known "Name Reactions', that have appeared in various
monographs or in the old Merck index. Some of these are so obvious
mechanistically to the modern organic chemistry practitioner that we have
in fact omitted them; for instance esterification of alcohols with acid
chlorides - the Schotten-Baumann procedure. Others are so important
and so well entrenched by name, like the Baeyer-Villiger ketone oxidation,
that it is impossible to ignore them. In general we have kept older name
reactions that are not obvious at first glance.
In some cases we have combined similar reactions under one
heading, for nstance the Hunsdiecker-Borodin-CrstoI-Firth decarboxy-
lative bromination. It is not a simple task to decide whether credit is due to




Foreword
the first discoverer of a reaction or to its developer. Often an improvement
on a method is more useful than the original discovery and usually one
reaction owes its inception to some previous discovery; non nova sed
nove.
Except in the case of reactions that have been known for a long time
under shared names, we often took the liberty to include in the title, as well
as in the references (here to save space), only the name of the major
author; for this we apologize to the co-authors, whose contributions are
often seminal. For reactions named after contemporary authors, we have
tried to consult the authors about choice of examples, etc. This led for
instance to the Mannich-Eschenmoser methylination.
Among the newer reactions we have chosen those that are not only
synthetically useful but at first glance not immediately obvious
transformations. Another criterion was the stereochemical implications of
the process. Yet, we admit our own bias in choosing from the plethora of
novel transformations that have appeared in the literature over the past 30
years or so. Space limitation was by necessity a criterion. Nevertheless we
have included approximately 450 name reactions and 2100 references.
We sincerely apologize if we have inadvertedly omitted important
reactions.
In all cases we have tried to include the first reported reference, a
reference to an experimental procedure and whenever possible a review
reference (joumal or Organic Reactions). In general, we did not include
references to books, series of monographs or to Organic Syntheses;,
chemists will of course consult these where available.
Furthermore, we have complied four indices, which should be helpful
to the reader:
1. A names index with cross references to multiple names;
2. A reagents index;
3. An Index to types of reactions, e.g. alkylations, stereoselective
reductions, cyclizatons etc.; and
4. Most important for the synthetic chemist is an index to the synthesis
of functional groups, e.g. synthesis of alkenes from ketones, as well as
conversion of ketones to alkenes.
We thank our families for their support and understanding during the
travail on this book Special thanks are due to my son Lawrence Hassner
for constructive suggestions and valuable help.
We are grateful to the TEVA Pharmaceutical Co. for support of this
project.
Alfred Hassner
Name and Unnamed Reactions 1
, A L O E R (lne) Reaction
Sigmatropc rearrangement with H-transler and C-C bond formation (Inter or intramolecular) and
chlral induction
.......
1 2 3 (62%)
O
Ph * +  Ph
O
1 Alder, K. Chem. Be" 1943 76 27
2 Usiell, V, J. Org Chem. 1973 36 1703
3 Achamatowicz, O J Org Chem 1980 45 1228
4 Smder, BB JOrg. Chem. 1982 47 745
5 HiII, R J Am Chem Soc. 1964 66 965
60ppolzer, W Angew Chem Int. Ed. 1978 17 476
Methyl 2.hydroxy.2-carbomethoxy-4-heptenoate (3). 3 A solution of dlmethyl
mesoxalate 2 (1.46 g, 10 retool) and 1-pentene 2 (0 70 go 10 mmol) in CH2CI 2 was heated at
140"C for 16 h. The solvent was removed and the residue distilled under reduced pressure. The
fraction collected between 90 and 105°C (0 5 tort) was diluted with Et20 (20 mL), washed with
water and dried The rescue after evaporahon of the solvent, gave on dlshllation 1 55 g of 3
(62%), bp 89-90°C (0 2 tort).

Related Pergamon Te of Interusl
Tetrehedron Organic Chernitn/ Ser:
CARRUTHERS: Cyclo==dd'on Reactions in Org=mlc SyntheeB
DEROME" Modem NMR Technique== f r Chemistry Reeeamh
DESLONGCHAMPS. Stereoelectroniў Effecte in Organio Chernitry
GAWLEY: A,/mmetriў Synthesis °
PAULMIER: Selenium Reagent= & Int=rrned'rates in Organic Synthesis
PERLMU'FrER: Conjugate Addition Reactions in Organic Sytthea
$1MPKINS: Sulphonea in Organic Synthesis
WLLIAMS: Synthesis of Optically Active Alpha-Amino Acld
WONG: Enzymes in Synthetic Organic Chemistry
BIOORGANIC & MEDICINAL CHEMISTRY
BIOORGANIC & MEDICINAL CHEMISTRY LETTERS
JOURNAL OF PHARMACEUTICAL AND BIOMEDICAL ANALYSIS
TETRAHEDRON
TETRAHEDRON: ASYMMETRY
TETRAHEDRON LE-I'TERS
Fu# details of a# Elsevier Science publicatonsffree specimen copy of any E/sewer Science
journal are avallab/e on request from your nearest E/sewer Science office
• In Preparation
Organic Syntheses
Based on
Name Reactions
and
Unnamed Reactions
Ao HASSNER
Department of Chermstry,
Bar.lien Universy, Israel
and
C. STUMER
Teva Pharmaceutical Industries,
Netanya, Israel
PERGAMON

4 Name and Umumed Reacnon Name and Unnamed Reactwn 5
A N G E L I - R I M I N I Hydroxamic Ac Synthess
Synthesis of hydroxamlc aclds from aldehydes and N sulfonyfhydroxylarrane, also used as a color
test for aldehydes
CHO .SO2NHO H ONHOH
CI CI
1 2 3
| Angeli, A Gazz. Chlal 1896 26 17(11)
2 RIn'dnl, E Gaz:z. Ch/m /a/ 1 9 01 31 84 (
3 Hassner A. J Org Chem 1 970 35 1952
4 Lwowsky, W Angew Chem Int Ed 1967 6 897
p'Chlorobenzohydroxamlў acid (3). 3 To an ice COOled solution of N hydroxybenzene-
suffonam=de 2 (365 rng, 2.1 retool) n MeOH, a | 93 M NaOMe solution (2 18 mL, 4 2 retool) was
added dmpwlse under st'flng A sok.,tion of P-chiorobenzaldehyde 1 (281 mg 2 mmol) in MeOH
(2 mL) was added and the reaction mixture was warmed to 20°C and stirred for an additional 2 h
The solution was concentrated in vacuum, diluted with Et20 (100 rnL) and extracted twice with 2
M NaOH The organic phase ytelded m0ure starling materials (45 rng) The aqueous phase was
acidified with 36% HCI to pH 7 8 and extracted twice with EtOAc The dried solubon (Mg$O4)
after evaporation of the solvent gave 225 mg of 3 (68%) mp 193 195°C The preduct gves a
red color with FeCI 3
A R B U z O V - M I C H A E L I S Phosphonate Synthesis
NI catalyzed phosphonate synthesis from phosphltes and aryl halldes Reaction of alkyl
hahdes with phosphltes proceeds without nickel salts
150 ° Ph t
N 2 + (EO)3P  [(EtO)3P] ,i N! 1 150 ° Ph (OEt)2
O
1 2 4 (94%)
reflux 
(Oro)3P + Me I  MeP(OIPr)= (%)
1 Mlchaehs A Chem Bet 18 9 8 31 1048
J Russ Phys Chem Soc 1906 38 687
2 Afouzov A
3 Balthazar, T M J Org Chem 19 8 0 45 5425
4 Montero J L Tetrahedron Lett 19 8 7 28 1163
5 Bnll ThB Chem Rev 1984 84 577
6 Kosolapov G M Org React 19 51 6 276
7 Kern MK J Org Chem 1970 36 5118
8 Redmore D J OJ Chem 1981 46 4114
Tetrakls(trlethylphosphlte)nlckel (0) (2) 3 Stirred N=Ct 2 (5 g) and trlethylphosphite 1
(60 mL) was heated and maintained for 1 h at 150 ° The sotld was filtered triturated with
MeCN and washed wth MeOH to gve 4 6 g el 2 mp 106 109°C
Dlethyl phenylphosphonate (4) To 2 (10 rag) in iodobenzene (10 0 g 49 mmol) at
160 ° was added slowly I (9 37 g 56 4 retool) The solution (red upon each addition of 1)
faded to yellow and Etl was distilled Vacuum distillation afforded 9 88 g of 4 (94%) bp 94
101°C (0 1 ram)

6 Name and Unnamed Reactwns Name and Unnamed Reacnons 7
A R E N S - V A N D O R P Clnnamaldehyde Synthesis
Synthesis ol clnnamaldehydes from aryl ketones
t C CX3zH s EtMgBr Ph CO-Me Pk /C=C OC2H s
  C
Me / \OH
(48%
2 1 3
3 H2/Pd Ph\ /CH.CH.OC2Hs HCI
BaSO"-"--'-" Id /C\oH  Ph (-CH C, HO
4 5
1 Arens JF v Dorp, AD Nature 1947 160 189
2 Isler, O HeN Chtm Acta 1956 39 259
3 Kell PS J Am Chem Soc 1959 81 4117
3"Phenyl-3-hydroxy-l-ethoxybutyne (3) 3 Ethoxyacetylene 2 (12 5 g, 0 18 tool) was
added to EIMgBr (from 4 34 g of Mg and 19 5 g EtBr In Et20) over 10 rain stlmng and ice cooling
After 15 rain acetophenone 1 (21 5 g, 0 18 mol) in EI20 (50 mL) was added over 1 h under ice
COoling Quenching (100 m/of 10% NH4Cl) and dist=llatlon g ave 15 g of 3 (48%) bp 98 100°C
(01 ram)
3"Phenyl-3-hydroxy-l-ethoxybutene (4) Hydrogenation of 3 (13 1 g 0 075 mol) in
EtOAc (100 mL) wdh Pd/BaSO4 (200 rag) gave after vacuum d=stlllahon 13 g of 4 (98 5%), bp
74 5 78°C (01 ram)
J]'Methylclnnamaldehyde(semlcarbazone) (5) 4 (1 0 g, 5 7 retool) m 0 1 N HCl was
rfluxed for 15 rain The cooled solution was treated w=th 0 1 N NaOH sencarbazide HCI
(500rag) and NaOAc (500rag) After adddon of EtOH (6 mL) and heating at 30°C the
semlcarbazone of 5 mp 205 5 206 5°C separated
A R N O T - E I S T E R T Homoiogation
Homologatlon of carboxyllc acids or ketones
Me Me Me Me
Me' -L ° Me 0 + MeM 0
/1-' e 2 3
1 Eistert B,Arndt F Chem Bet 1927 60 1364
2 Barler F Helv ChlmActa 1940 23 523
3 GokeI, G Synthesis 1976 181
4 Aama T Chem Pharm Bull 19 81 29 3249
5 Smith, AB J Am Chem Soc 1986 108 3110
6 Welgand F Angew Chem 1960 72 535
7 Bachmann, W E Org React 19 4 2 I 38
3,3,5 and 3,5,5-'rrlmethylcycloheptanone (2) and (3) 2 "ro a cooled solution of 3,5 5-
tnmethylcyclohexanone I (100 g 0 71 tool) in MeOH (225 mL) and 50% KOH was added in
small podlons nltmsomethylurea (74 g, 0 68 tool) under stlrnng and cooling (0*C) After each
addition the solution was agowed to become colorless before the next portion was added The
reaction mlxlure was allowed to stand for several hours and was filtered and neutrahzed with
AcOH The solvent was removed and the residue distilled to afford a mixture of 2 and 3, bp 70
95°Cll 1 mm
For an alternate procedure for generation of dlazomethane from hydrazlne chiomform and
KOH see ref 4

8 Name and Unnamed Reaction Name and Unnamed Reactions 9
A T H E R T O N - T O O O Phosphoramldate Synthesis
Synthesis of phosphoramidates from formamldes and dlalkyl phosphite.
 CeHs-I-P(CC2H) a
1 O 2 H-C-O
/
CHs'NH'Ic(OC"J
3
1 Alhedon, F.R.,Todd, A.R.J. Chem. Soc. 1945 660
2 Wadswodh, W.S. J.Am. Chem. Soc. 1982 84 1316
3 Zwle=ak, A. Synthesis 19 8 2 922
4 Lukanow, L K. Synthesis 1985 971
Dlethyl N-Phenylphosphoramldate (3).4 To an ice cooled stirred suspension of
formylantlide 1 (0 605 g, 5 retool) in CC[4 (25 mL) was added a solution of 30% NaOH (10 mL) and
benzyltdethyiammonium bromide (0 2 g). Diethyl phosphate 2 (0.828 g, 6 retool) in CCl4 (5 mL)
was added dropwise. Stirring continued for 1 h at ice bath temperature and 4 h at room
temperature. The separated organic layer was deled (Na2SO4) and the solvent removed in
vacuum to give cnJde 3, which was puntied by recrtalllzation to yield 0.687 g (60%), mp 96-
97°C.
A U W E R S Fla.'one synthesis
Synthesis ol benzopyran-4-ones (flavones) from o-hydmxychaicones or from benzofuren-3-
ones
O
+ phCHO EtOH --"- CH - Ph 
I 2 C 3
0
4 5 (70%)
1 Auwers, K Chem. Ber. 1908 41 4233
2 Minton, T.H. J. Chem. Soc 1922 121 1598
3 Ingham, B.H J. Chem. Soc. 1931 895
4 Acharya, B C J. Chem Soc. 1 9 4 0 817
7.Chioro-2-benzylldenecoumaran-3-one (3) 2 A sotuticn of coumaranone 1 (2 0 g, 12
mmol) and 2 (3 2 g, 30 mmol) m EtOH was heated at 60°C and 36°/,, HCI (1 mL) was added siowty
On cooling, 3 cr,jstalhzed The filtered and dried product melted at 143°C
7-Chloro.2-benzylldenecoumaran-3-one dlbromlde (4). To a solution of 3 (5.0 g, 20
mmol) in CHCI3 (10 mL) was added a solution of bromine (3 2 g, 20 retool) in CHCI 3 (10 mL)
After 24 h the solvent was removed at 20-25°C and the residue recrystalhzed from HOAc, mp
1470C.
8-Chlorollavonol (5) A solution of 4 (2 0 g, 5 retool) in EtOH (150 mL) was treated with 0 1
N KOH (100 mL). The mixture was boiled for 10 rain and the preduct was preopitated with water.
Recrysalhzatlon from HOAc yielded 1 g of 5 (70%), mp 187°C.

10 Name and Unnamed Reaction Name and Unnamed Reactions 11
B A E R - F I S C H E R Amino sugar synthesis
Synthesis of 3-mtro and 3-amino sugars by aldol condensation of sugar-derived dlaldehydes
with nitmalkanes.
H OH NO=
OMo OMo
3 4 (19%)
1 Baer, HH.,Fischer, H.O.L ProNat-Acad. ScLUSA 1958 44 991
2 Baer, HH. Adv. Carbohydr Chem. 1969 24 67
3 Brlmacombe, JS J. Chem. Soc Perldnl 1974 62
4 SantoyooGonzales, F. Synlett 1990 715
Methyl 2,4"Ol'O'acetyl'3,8-dldeoxy-3-C-methyl.3.nltro..L.gluўopyrannoslde
(4) .3 Methylo-L-rhamnopyrannoslde 3 (100 g, 0.55 tool) in water (1000 mL) was treated with
NalO4 (200 g, 0 83 tool) at 20°C. After 3 h NaHCO 3 was added, the mixture poured into EtOH
(4000 mL) and filtered The filtrate was concentrated and extracted wh hot EtOH. The extract
was cooled, filtered and treated with nltmethane (104 5 g, 1.4 mol) followed by a solution of Na
(12 g, 0.52 at. g) in EtOH (750 rnL). After 4 h at 20°C the solution was treated with CO2, littered
and concentrated The mixture was treated wth pyrdlne (400 mL) and Ac20 (300 mL) at 20=C
for 12 h. Workup left a residue which dissolved in Et20 petroleum ether (1:1) (500 rnL) and
cooled afforded 36 g of 4 (19%), mp 137-138oc, [O.]D,,,.130o C (c 1).
B A E Y E R Oxlndole Synthesis
Synthesis of oxlndole from o-nitrophenylacetates.
NO=
H
1 2 (100%)
1 Baeyer, A. Chem Bet 18 78 11 582
B A E Y E R DlalyImethane Synthesis
CH
HzSO4
+ OCH - CH3 -----.-I,- H3 C CH3
1 2 3
1 Baeyer, A. Chem Ber 1872 5 280
2 Matsuda, K J Org Chem 1963 27 3256
3 Schnell, W Angew Chem Int Ed 1 962 75 622
Oitolylethane (isomers mixtures) (3) 2 To ice cooled toluene 1 (557 g, 642 mL) was added
simultaneously acetaldehyde 2 (77 g, 1 67 mol) in 420 mL o( 1 and 95% H2SO4 (655 g) in 2 h.
After stlmng for 1 h, water (1000 mL) was added cautiously and the organic layer washed (5%
NaOH, water). Vacuum distillation gave 101 g of 3 (88%), bp 150°C (10 ram).

12 Name and Unnamed Reactions Name and Unnamed Reac,ons 13
B A E Y E R Pyrldine Synthes=s
Synthesis of pyddines from pyrones
O OMe OMe
MeO M 2,SO MeO (NH4)2CO3
I. • 4 
"-OMe 2. HClO4 "- "''Me Me
1 2 3
1 Baeyer, A. Chem. Ber. 1 91 0 43 2337
2 Nenitzescu, C.D Uebigs Ann.
1959 625 74
3 Cavallied, LF. Chem. Rev. 1947 41 525
4 Dimroth, K Angew. Chem. 1 96 0 72 331
2-Methyl-4,5-dlmethoxypyrldlne (3).2 1 (70 g, 0 2 mol) and dlmethyl sulfate (31 g, 0 25
mol) were heated for 2 h at 50oc and poured into 2x excess of ice cold 20% HCIO4. After 2 h the
product was filtered and added to 10% (NH4)2CO3 (175 mL), saturated wdh (NH4)2SO 4 and
extracted with EtOAc. Evaporation and distillation afforded 3, bp 75-80°C (1 ram), hydrochiodde,
mp 164°C.
B A E Y E R - O R E W S O N Indoxyl Synthesis
Conversion of o-nltrobenzaldehyde and ketones to indoxyls.
1 2 (46%)
1 Baeyer, A,Drewson, W Chem. Ber. 1882 15 2856
2 Hinkel, L E J. Chem Soc 1932 985
3 Hassner, A. Tetrahedron Lett 1962 975
B A E Y E R - V I L L I G E R Ketone Oxidation
Synthesis of esters or lactones from ketones with retention of configuration
o
HzOz
C
CH3
1 2
1 Baeyer, A.,Villiger, V Chem Ber 1899 32 3625
2 Hassner, A. J Org. Chem. 1978 43 1774
3 Sarapanarni, C.R. J Org. Chem 1986 51 2322
4 HassaI, C.H Org React. 1957 9 73
Blcycllc lactone (2). 2 To1 (0 79 g, 5 mmol) in 90% AcOH (5 mL) at 0°C was added 30% H202
(2.5 niL) in 90% AcOH (3 mL), kept at 0°C for 24 h poured into H20 and extracted wth petroleum
ether (bp 40-60°C). The organic extract was washed (NaHSO3, H20) and evaporated to give 0.57
g of 2 (65%).
BAEYER * VlLLIGER Trdlatlon
Intreductlon of a trphenyimethyl group into an aromatlc dng OH
HS04 
PhOH + Ph3CCH HOAc, rt  3 (90%)
1 2 CPh 
H2SO 4 cat H
1 + 2  4
loo,, CPh 3
1 Baeyer, A.,Villiger, V Chem Ber. 1902 35 3013
2 Hardy, D.V.M. J Chem. Soc. 1929 1000
3 Shulgin, AT. J Crg. Chem 1962 27 3868

15
14 Name and Unnamed Reactions Name and Unnamed Reactions
HO OH
PhCOOIPh
O
4 (82%)
Baker, W.
Venkataraman, K
B A K E R - V E N K A T A R A M A N Flavone synthesis
Rearrangement of aromatic keto esters of phenols to flavones
PhCCCt PhCOO,OCOPh
 cOMo PhMo, 10o" 
2 3 (73%)
HOAc  HOPh
Na OAc
O
5 (90"/°)
J. Chem Soc. 1 9 3 3 1381
J. Chem. Soc 1 934 1767
3 Krarnm, E J. OrgChem 1984 49 3212
4 Levine, E. Chem. Rev. 1954 54 493
Resacatophenone dlbenzoate (3). 1 Resacetophenone 1 (30 4 g, 0 2 mol) benzoyl
chlonde 2 (5 2 g, 0 4 mol) and pyrtdme (60 mL), were heated on a steam bath for 15 rain The
mixture was treated wdh water, dll HCI and then EtOH to give 53 g of 3 (73 6%), mp 80°C
(MeOH).
1-Phenyl-3(2-hydroxy-4-benzoyphenyl)-propandlone-l,3 (4) A mixture of 3 (20
g, 55 mmol), PhMe (200 mL) and K2CO3 (60 g) was stirred on a steam bath for 2 h. After usual
wolt up 16 5 g of 4 (82%) was obtained
7-Hydroxyflavone (5). 4 (5 g, 13 8 mmol) in AcOH (50 mL) and NaOAc (10 g) was boded for
6 h, then poured into water to g=ve 2 6 g of 5 (90%), mp 240°C
B A L L Y - S C H O L L Benzanthrene Synthesis
Synthesis of polycondensed aromatics from antraqulnone and tnols.
OH 
O + O
1 2 3 (S%)
1 Balty, 0 Chem Ber 19 0 5 38 194
2 ScholI, R. Chem Ber 1911 44 1656
3 Warren, F L J Chem Soc 19 38 401
4 Allen, C F H Org Synth Coil Vol II 62
B A L S O N Alkylatmn
Alkylatlon of aromatics with HF (see FnedeI-Crafts)
+ 18h/15C
1 2 3(74%)
1 Balson, M Bull Soc Chum Fr
2 Price, C S J Am Chem Soc
3 Smith, W T Org Synth
4 (17%)
1879 31 539
1939 61 663
Coil Vol IV 702

16 Name and Unnamed Reacnons Name and Unnamed Reactions 17
B A M B E R G E R Iole cleavage
Cleavage of =mdazoles to enediarntdes, useful in synthesis of 2substituted lmdazoles.
cooc
1 Bamberger, E Lebgs Ann 189 3 273 342
2 Babad, E. J. Heterocycl Chem 1 9 6 9 6 235
3 Grace, ME J Am Chem Soc. 1980 102 6784
4 Kimoto, H J. Org. Chem 1 978 43 3403
5 Altman, J J Chem Sc Perklnl 1984 59
Ethyl 4,5-Dlbenzamldopent.4-enoate (2)5 Ethyl 3-imldazol-4(5)-ylpmpanoate 1 (9.2
g, 54 mmol) in EtOAc (140 mL) was treated with benzoyl chloride (15 7 g, 112 retool) in EIOAc
(40 mt) and 1M NaHCO3 {380 mL) added simultaneously In 1 h under ice-cooling. The
reaction mxture was stirred for 1 h, then a further portion of benzoyl chloride (15 7 g, 112
mmol ) in EtOAc) and 1M NaHCO3 (280 mL) was added m the same manner, followed by an
additional portion of 1M NaHCO3 (200 roLl The reaction mixture was stirred for 24 h, then the
organic layer was separated, concentrated, and the residue dissolved In THF (300 mL) The
THF solution was stirred wth 10% NaHCO3 (600 mL) for 24 h to decompose any N-Iormyl
intermediate and to remove benzoic acid Extraction wth EtOAc, drying (Na2SO4), solvent
evaporation and recrystalhzation of the residue from EtOAc hexane afforded 16 24 g o! 2
(84%), mp 128-129oc
B A M B E R G E R Phenylhydrox'ylamlne Rearrangement
Rearrangement of N-arylhydmxylamlne to amlnophenol
H-N-OH NH
 10% H2SO4  H2"---'---''O
+ OH
1 2 (7o%)
1 Bamberger, E. Chem. Ber 1894 27 1348
2 Hughes, E D Guart Rev (London) 1 925 6 45
B A M B E R G E R Benzotnazlne Synthesis
From pyRIvic aod hydrazone 2 and aryldlazoamlne salts 1
, NH2
o" N=*  H=SO-----
OMo ' OMo
1 3
1 BalTrger, E Chem Ber 1892 25 3201
2 Abramovitch, RA J Chem Soc 1955 2326

18 Name and Unnamed Reactions Name and Unnamed Reacnons 19
BAMFORD . STEVENS . CAGLIOTI. SHAPIRO Otefination
Conversion of ketones to olefins v|a tosyl hydrazones wth NaOR, LAH, LDA or BuL|
N'HN-Ts 1 2 (9t%)
.,,,,,=N NH T$
3 4 (e1%)
1 Bamford, W, Stevens T, J Chem Soc 1 9 5 2 4735
2 Famum, DG J Org Chem 1973 28 870
3 Nlkon, A J Org Chem 19 81 46 4692
4 Stedler, H Helv Ch/m Acta 1984 67 1379
5 Shap|ro, RH OrgReact 1976 23 405
6 Caglmtl R Tetrahedron Lett 1962 1261
7 Caglmti, R Tetrahedron 1963 19 1127
8 Nlkon, A J Org Chem 1970 35 1509
(E)-Splro[12,11]tetracos.13.ene (2).3 Splro tosylhydrazone 1 (0 275 g, 0 53 mmol) In
diglyme (8 mL) under N2 was treated wth MeONa (011 g, 2 mmol) After1 h reflux the mixture
was extracted wth Et20, the extract washed (brine) and evaporated to afford 0 t6 g of 2 (91%),
mp 64 66°C (pentane)
Corlolane derivative (4).8 To a suspension of LIAIH4, (0 5 g, 13 2 mmol) in THF (12 mL)
under N2 was added 3 (0 5 g 1 14 retool) After 24 h reflux the mixture was washed (water.
15% NaOH and water) extracted wth Et20 and the organic extract concentrated The oily
residue, 0 22 g of crude 4 (81%) was purified by sublimation and recr'/stalhzation (EtOH/H20)
to give 0 11 g of 4 (40%), mp 101 1015°C
B A R B I E R Reaction
In sdu Grignard generation in the presence of an electrophde
1 2 (70%)
Me.. 
M,S. M ч ____/---St  M. "s''-'- (94%)
1 Barbler P CR 1899 128 110
2 Gngnard V CR 1900 130 1322
3 Ashby, R Pure&Appl Chem 1980 52 545
4 Huang. XZ TetrahedronLett 1988 29 1395
5 Blomberg C Synthess 1977 18
6 Hassner, A J Organomet Chem 1978 156 227
Cyclopentanone (2). 5 Magnesium (I 2 g 0 05 at g) was heated under Ar After cooling
Et20 (10 mL) was added followed by 5 cyano I iodobutane 1 (10 g, 0 05 mol). so that the
mixture reftuxed gently A slight coloration disappeared on addlt=on ol a few drops of 1 2
dlbromoethane The reaction mixture v.as stirred lot another 12 15 h at 20 25°C and
hydrolyzed (ice NH4CI) The Et20 layer was washed wth NaHSO3 solution The solvent was
evaporated and the residue refluxed 24 h in a solut=on of oxalic acid (10 g) in water (60 mL)
After extraction with Et20 evaporatmn of the solvent and d=stdlation there was obtained 2 56
3 4 g of 2 (61 79%). bp 130 131°C

20 Name and Unnamed Reactions Name and Unnamed Reactions 21
BARBIER - WIELAND Degradation
A multi-step procedure for chain degradation of esters
 I  OzMe
HO' Ao20 -- NalQ 
1 3
4 (e0%)
1 Barbler, P CR 1913 156 1443
2 Wieland. E Chem Bet 191 2 45 484
3 Sarel S J Org Chem
1959 24 2081
4 Fetlsson, M CR 1981 252 139
5 DjerassI, C Chem Rev 1948 38 526
3cў-Acetoxy-24,24-dlphenylchol-23-ene (3).3 Methyl 3cў hydroxycholanate 1 (78 g,
0 2 mol) was refluxed wtth PhMgBr 2 (3 mol) in benzene for 24 h The product was acetylated
with Ac20 (60 roL) in pyddlne (100 roL) and after evaporation of the solvents, the residue was
refluxed In AcOH (200 mL) for 20 h Cooling gave 3, recrystalhzated froro Me2CO. rop 160°C,
(X2D0 = +67 °
3-o.-Acetoxynorcholanlc acid (4). 3 3 (2 g, 3 7 rorool) In acetone (200 mL) was treated with
FluO4 (120 mg) and 5% NalO4 at 20 ° NalO4 (4 5 g, 0 021 mol) was added m portions over 4 h
A few roL of IPrOH was added, the catalyst was filtered, the solvent evaporated and the residue
treated wth water Extraction wth Et2 O and reextracton wth aq Na2CO3 gave after
chroroatography (SIO2 Phil) 1 5 g of 4, froro acetone 1 20 I 25 g (80 83%), rop 177 178oc,
(x0 = 51o '
B A R T - S C H E L L E R Aromatic arsonylat=on
Aroroatic arsonylat=on substlttut=on of an arooroatic amine by As wa dlazomuro salts
HNO2 ' v. AsOsNa 3
NO NO NO
1 2 3 (75%)
1 Bad, H Ger Pat 1 91 0 250 264
Frd 1910 10 1254
2 Scheller Bnt Pat 1927 261 026
CA 1927 21 3371
3 Ruddy AV JAm Chem Soc 1942 64 823
4 Cowdr'/ WA CJuart Rev 1952 6 363
S C H I E M A N N AromatlcFluonnatlon
Substitution of an aromatic amino group by fluorine via a dazonlum salt using fluoroborates
NH 2 2 HBF, 50" F27O/o
4 5
5 Schleroann, G Chem Ber 1927 60 1186
6 Finger GC J Org Chem 1962 27 3965

22 Name and Unnamed Reactions Name and Unnamed Reactions 23
B A R T O N Nlmte photolysls
Long range functlonahzatk>n of alcohols via nitrites leading to "t-hydroxy oxlmes
NO
O /OAc HON O.. .O/
H_Oyl 0,./ ..... -H
0. v ,. ,,- .., ---'--0,,,,,,,.
1 Barton, DHR JAm Chem Soc 1960 82 2640
2 Barton, D H R J M Chem Soc 1 961 83 4076
3 Barton D H R Pure Appl Chem 1 9 6 8 16 1
4 Baldwln, SW J Am Chem Soc 1982 104 4990
5 Barton, D H R Aldnchmca Acta 1 9 9 0 23 3
Aldoaterone acetate oxlme (3) 1 Cortlcosterone acetate 1 In d/pyndlne was treated
with excess of NOCI at 20°C to give cortcostemne acetate-11 nitrite 2, mp 176°C cz D = 316 o
(CHCI3) The ntnte (4 g) in PhMe (200 mL) was rradated at 32°C under pressure of N 2 for 2 5
h The IR band of nitrite disappeared A crystalhne product was obtained 885 mg of 3
(21 2%), mp 175 194°C, cz D = +198oc
B A R T O N Deamlnatlon
Free redcal deamlnation of pnmary amines via isocyanldes
O O
HC-O-CCH 3 pTsCI
H-jC(CH2 s-CH;z-NH --- H-j C ( CH 2 i.,H-a'WH .CHO
1 2
n Bu3SnH
H3C(CH2)eCHi-N ='=C AIBN = H3C(CH2)e'CH3
3 (95%) 4 (81%)
I Barton, DHR J Chem Soc Perkml 1980 2657
2 Swlndell C S J Org Chem 19 9 0 55 3
3 Barton, D H R Aldnchmca Acta 1 9 9 0 23 3
1.Formareldooctadecane (2) 1 To a saturated solution of octadecylamlne 1 (2 g, 7 43
mmol) In Et20-pentane was added acetic formic anhydride (0 8 g, 10 mmol) dropwise at 0*C
.aJter 1 h pentane was added to tUrblddy and the mixture was cooled to 20°C Formamide 2
was filtered and recrystallzzed from MeOH to give 2 g of 2 (91%), mp 66°C
1-1socyanooctadecane (3) A solution of 2 (0 712 g, 2 39 mmol) in pyndlne (30 mL) was
treated with pTsCI (0 77 g, 4 05 mmol) and after 2 h was poured onto ice water The precipitate
was filtered, washed and recrystaltlzed (CHCI3 MeOH) to yield 0 635 g of 3 (95%), mp 35°C
Octadecane (4) A solution of 3 (0 279 g 1 mmol) and azomobutyrondnle (AIBN) (0 1 g) in
dry xylene (50 mL) was added dropwlse to a solution of tn n-butyl stannane (0 64 g, 2 2 mol
equlv) A solution of AIBN (0 I g) in xylene (50 mL) was slowly added at 80°C over 5 h The
solvent was removed in vacuum the residue dissolved in pentane and iodine in pentane was
added until the k)dlne colour persisted The solvent was evaporated and 4 was isolated by
preparative TLC (silica gel pentane) Sublimation in vacuum gave 0 205 g of 4 (81%), mp 29'C

24 Name and Unnamed Reactions Name and Unnamed Reactions 25
B A R T O N Decatboxylat=on
Decad:x}xylatlon of a roixed anhydride (thlohydmxamlc-carboxylic) and interception of radicals as
a sulfide, selenlde or bromo derivative,
CI+j(CH---COCI NaOoN S - - - PhS- SPh
+    = (CSPh
1 /2 3 &4 5 ў74%)
BN, 1" VV
O
6 7 H 8 9 (75%)
1 Baon, D H R. J. Chem. S. Chem. mmun. 1 983 939
2 Ba,DHR. TetrahedmnLe#. 1984 25 5777
3 Ba, D H R. Tetrahedmn Le#. 1 985 26 5939
4 Baon, D.H.R t A 1990 23 3
Pentadecyl phenyl thloether (5). 2 Froro palroltoyl chloride and the hydroxaroic sodiuro
salt 2 there was obtained the ester 3 which by heatin in neat PhSSPh (30 equivalents)
afforded 5 in 74% yield.
2-Broroonaphthalene (9).3 In the saroe roanner the acyl chiodde 6 was reacted with
hydroxaroic derivative 7 to give the rolXed ester 8, which heated in BrCCI3/PhCI in the presence
of azoisobutronltnle (AIBN) at 130°C afforded 9 In 85% yield.
B A R T O N - K E L L O G G Olelinatton
Olefin synthesis (tetrasubstltuted) from bydrazones and thioketones via &3-1,3,4-
thiadiazolines.
Pb (OAc. S Ph S Ph
1 2
/.O HClOEt)3 2 Ph
3 4 188%) 5 (90%)
1 Barton, D H.R. J. Chem. Soc Perkm I 1 9 7 2 305
2 Barton, D.H.R. Chem. Soc. 1 970 1225
3 Kellog, R.M. Te'ahedron Lett. 1 970 1987
4 Kellog, R M. J. Org Chem. 1 972 37 4045
5 Badon, D.H+R. J. Chem Soc Perklnl 1974 1794
Dlphenyldlazomethane (2). 5 Froro lead tetraacelate (889 rog, 2 romol) in CH2CI2 (5 mL),
1 ((295 mg, 1.5 romol) and TEA (5 roL) at -20°C was obtained 291 mg of 2 1100%).
(-) Thlocarophor (4) (-) Camphor 3 (15 2 g, 0.1 mol) and lnetbyl orthofon'rlate (15 9 g,
0 15 mol) n MeOH (50 mL) were saturated sfmultaneously with H2S and HCI gas over 1.5 h at
0°C. The rocdure poured onto ice afforded 4 Chromatography arid sublimatn at 85°C (20
roro) gave 7.12 g (88%) of 4, mp 116°C, c) 4 - -21 4 °
(-)-2-Dlphenylethylenecarephane (5). 2 (585 mg, 3 romol) (froro 1, lead tetraacetate
and TEA in CH2CI2 at -20°) s and 4 (505 rag, 3 romol) in THF (5 mL) were heated to reflux
under N 2 for 3 h. After chroroatography, the product was refluxed with Ph3P (870 rog) In THF
(5 mL) for 16 h and evaporated The residue In petroleuro ether was treated with I roL of Mel
(exolhermic) and St,Ted 2 h Chroroatography (silica) afforded 545 rog of 8 (90%), mp 69 5 -
72 50C (EtOH).

26 Name and Unnamed Reactwns Name and Unnamed Reactwns 27
B A R T O N * M C C O M B I E Deoxygenatlon
Deoxygenaton of secondan] alcohols to hydrocarbons (via xanthates)
H 1 C I ROCSM
OH, .........
04%)
[O ( ) .... ........ AIBN 120  [O
O O
1 Barton, OHR.McComble. SW J Chem Soc Petkln/ 1975 1574
2 Cnstol, S J J Org Chem
1982 47 132
3 Barton, DHR Tetrahedron 1986 42 2329
4 Cnch, D AldnchmlcaActa 1987 20 36
5 Hartwlg, W Tetrahedron
1983 39 2609
6 McClure, CK J Org Chem 1991 56 2326
1,6-Anhydro-2-deoxy-3,4-0-1sopropylldene.D-galatose (4).1 A rolxture of I 6
anhydro 3 4 0 lsopropylldene  D-galactose 1 (900 rog 4 45 romol) Nail dispersion (80%,
270 mg), iroK:lazole (5 mg) and THF (12 roL) was stin'ed for 0 5 h at 20'C CS 2 (2 mL) was
added and the stlron was continued |of 1 h Methylation (Mel 0 5 roL) and usual work up
gave a yellow oil (xanthate 2) which was healed under reflux In PhMe (40 roL) under Ar during
addition over 1 h of a solution o! trlbutylstannane 3 (1 6 g, 4 5 mmol) Refluxlng was
continued for 16 h then the rolxture was evaporated and chromalographed on silica gel
Evaporation gave 780 mg of 4 (94%) bp 75°C (2 ram), cў22D= 141" (c 3 5)
B A U D I S C H Nltrosophenol Synthesis
Synthesis of o-nltrosophenols
O (NH,) (F.(CN)s __M.j ) [CH
1 Baudisch, O Naturwssenschaften 1939 27 769
2 Baudtsch, O Sctence 19 4 0 92 336
3 Baudisch, O JAm Chero  1941 63 622
4 Cronhelro, G J Org Chem 1947 121,7,20
o-Nitrosophenol (2). 3 An aqueous solut|on of pentacyanoamlne ferroate, ammonium salt (2 0
g) cooled In tced water, was treated with Phil (50 roL), hgrolne (50 mL) and hydroxylaroine (2 0 g)
Under shalang hydrogen peroxide (4 0 roL) was added and after I h the organic layer changed color
Io deep green due to the formation o| 2.
2-Nitroao-4-chlorophenol copper chelate (4) 4 A solution of IPchlorophenol 3 (12 85 g,
01 tool) In AcOH (30 mL) diluted wlth water (50 roL) was treated with NaOAc at pH = 4 2 To this
modure was added a solution of NaNO 2 (17 3 g, 0 25 tool) and CuSO4 (12 5 g, 0 05 tool) In water
(500 mL) After 24 days at 25°C, filtration of the precipitate afforded 80-95% of copper chelale 4 In
90% punty The product was crystallized froro a roodure EtOH CHCI3 (2 3)

28 Name and Unnamed Reactions Name and Unnamed Reactions 29
BAYLIS - HILLMAN Vinylalkylaon
Amine catalyzed conversion of acnates to a-(hydroxyalkyl) ac/lates or of vinyl ketorms to a-
(hydroxyalkyl) vinyl ketones.
o OH O
+  C02Et
Me-CHO I1 CO2E! OABCO CO2Et
II
+ DABCO
1 Bayits, A.B.,Hillman, M.ED. Ger. Pat. 2155113C.A. 1972 77 3417
2 Basavalah, D. TetrahedronLett. 1988 27 2031
3 Basavaiah, D. TetrahedronLett. 1987 28 4591, 4351
4 Basavalah, D Tetrahedron Lett. 1 990 31 1621
4-Hydroxy-3-methylenetrldecan-2.one (2),2 A solution of decanal 1 (3.12 g, 20
mmol), methyl vinyl ketone 2 (1.4 g, 20 mmol) and 1,4-dazabicyclo.octane (DABCO) (0 33 g,
3 mmol) in THF (5 mL) was allowed to stand at 20°C fir 10 days The reaction mixture was
taken up in Et20 (25 mL), washed with 2N HCI, NaHCO3 solution and dded (MgSO4).
Punfication by colum chromatography (5% EtOAc In hexane) and distdlation gave 2.95 g of 2
(65), bp 117-120oc/0.5 ram.
B E C H A M P Arsondatlon
Arsonilation of phenols and anilines.
1 2 130%)
'OH + AsO, H3 "zt [OH (33%)
AsO 3 H
1 Bechamp, A.J CR. 1863 56 1172
2 Ehdlch, P Chem Ber 1907 40 3292
3 Brown, H P J Am Chem Soc. 1 9 3 4 56 151
4 Hamilton, C S Crg. React 1 9 44 2 428
1.Amlno-2.naphthalenear$onlc acid (2). 3 cў-Naphthylarnlne 1 (50 g, 0 34 mol)was
melted by heating to 150°C and arsenic acid (10 g, 0 07 mol) was added under stirring. The
rnxture was mainta=ned for 10 m=n and cooled to 75-90°C it was then heated to 165-170°C
under constant stirnng and was ma=ntalned for 10-15 mm at this temperature. After cooling to
100°C, the mixture was poured =nto 0 5 N NaOH (250 mL), the sodium salt solution was treated
with Nonte, filtered and the product p.reclpdated with 6N HCI at pH 3. Purification vta the sodium
salt afforded 5-6 g of 2 (16-32%), mp 175-176°C

30 Name and Unnamed Reacnons Name and Unnamed Reacnons 31
B E C K M A N N Rearrangement or fragmentation
Acid catalyzed rearrangement of oxlmes to amides or cleavage of oxlmes to nltnles
1 IOO"o. lh
2 (9S%)
p/r, 0 ° --
3 SnSu 4 (73%)
NOH
Ph-(H  IV PC Ph OH Cl+Me(
1 Beckmann E Chem Ber 1886 19 988
2 Conley R T J Org Chem 1 9 6 3 28 210
3 Eaton PE J Org Chem 1973 38 4071
4 NlshlyamaH Tetrahedron 1988 44 2413
5 Johnson, C R J Am Chem Soc 19 9 0 112 6729
6 Hassner A Tetrahedron Lett 19 6 5 525
7 Popp, I Chem Rev 1958 58 370
8 Heldt W.Z Org React 19 6 0 11 1
ў-Caprolactam (2) 3 To MeSO3H (360 g) was added under dr,/conditions and stlmng P205
(36 g) until all dissolved (1 2 h) The product is stable if stored d/ 1 (2 g, 20 rnmol) was added
to the MeSO3H P205 (50 g) under efficient stlmng After I h at I00°C, the cooled mixture was
quenched wth saturated NaHCO3 (200 mL) Extraction with CHCI3, evaporatK)n of CHCI3 and
recrystallizatlon from petroleum ether gave 1 92 g of 2 (96%), mp 85 68°C
oPHexenenltrlte (4) 5 To oxime 3 (99 mg 0 5 mmol) in CH2CI2 (2 mL) was added P205 (70
mg, 0 5 mmol) at 0°C After I day stimng at 20=C, Et20 (2 mL) and NEt3 (012 mL) were added
Washing with brine and chromatography on silica gel afforded 43 rag, of 4 (73%)
B E N A R Y Conjugated Aldehyde Synthesis
Formation of polyunsaturated aldehydes from vnyl haildes and enarntnoaldehydes
1 2 3 (57%)
1 BenaP/,E ChemBer 1930 63 1573
1958247 1744
2 Normant H C R
Hetv Chlm Acta 1 972 55 2363
3 Schless, P
4 N;ff F Hetv Chlm Acfa 1974 57 1317
(E,E) and (E,Z)-2,4-Decadlenal (3) 4 1 Bromo 1 heptene 1 (8 85 g 50 mmol) in Et20
(20 mL) at 10°C was treated wth U (0 7 g 01 at) in Et2 O (20 mL) Nter 2 h stlmng at -8 to
12°C, (E) 3 (N methyl N-phenylamino) acrolen 2 (8 05 g 50 mlll) n Et2 O (50 mL) was added
over 15 Inn The reaction mixture became doughy Stlmng was continued for 2 h while the
temperature rose to 20°C Excess LI was filtered and the Inxture was poured onto iced 20=/,
aqueous H2SO 4 Extraction with Et20, washing and evaporation gave 4 32 g of 3 (57'/0), bp
57 61°C (0 01 ram), 14% (E Z) and 86% (E E) by GC (20% Carbowax 20M 200°C)
3 (via Grlgnard reagent) 1 (4 42 g, 25 retool) and Mg (0 6 g, 25 mat) in THF Iollowed by 2
(4 02 g, 25 mmol) and usual work up gave 1 32 g of 3 (33%) bp 95 103°C as a mxture of 12%
(E Z) and 88% (E E)

Name and Unnamed Reacnons
32 Name and Unnamed Reacnons
B E R N T H S E N Acndlne synthesis
Acndne synthesis from dlphenylamlne and carboxyhc acids
1 H 2 3 (25%)
NH 
4F. 155 175 °
+ HCOOH ll "
1 Bernthsen A LlebFgsAnn 1878 192
2 Popp FD J Org Chem 1962 27 2658
3 Albert F J Chem Soc 1948 1225
3 Buu Hol M P J Chem Soc 19 5 5 1082
5-Phenylacrldlne (3) 1 Dlphenylamlne 1 (16 9 g 0 1 rnol) 2 (12 2 g, 0 1 reel) and anh
ZnCI 2 (41 g 0 3 reel) were heated for 10 h at 260°C The brown solid dissolved =n warm alcohol
was poured into conc NH4 OH (50 mL) and a fief 24 h diluted with 500 ml of water Fdtratlon
washing and extraction with benzene decolonzatlon with charcoal and evaporation n vacuum
afforded 8 9 g of 3 (25%)
2-Amlnoacrldlne (6) 3 4 (37 g 0 2 reel) glycerol (150 g) formic acid (9 2 g, 0 2 mol) and
conc HCI (17 ml) were heated to 155=C maintained at this temp for 30 rnln and heated to
175°C for 30 mln The product was treated with sodium acetate (10 g) in water (400 mL) After
filtration of N N dlphenylproflavlne the filtrate was treated with NaOH solution and boiled to
precipitate the crude product After recrystalhzatlon from alcohol there was obtained 6 23 g
(59%), mp 216°C
B I G I N E L L I Pydmldone synthesis
Pyrim=done syrdhesis from urea, an aldehyde and a J-keto ester
H
/NH2 /CH.j heat Oўr. N
_ + O=C\ 
0
CNH2 H HN COOCH$
CsHs
1 2
+
4 (::)
C6Hs-C-CH2 cOOC2Hs
1 BIglnellI, P Chem Ber 1891 24 2962
2 Folkers, K J Am Chem Soc 1933 55 3361
3 Swett, I J Am Chem Soc 1973 95 8741
4 Zaugg, H,E Org ReaCt 1968 14 88
2.Keto.4.methyl.S.carbetoxy.6.phenyl.l,2,3,4.tetrahydropyrlmldlne (4) 2 To
cooled AcOH (10 mL) at 10°C was added under stlmng, urea I (3 g, 68 mmol), Me CHO 2 (3 3
g, 75 mmol) and ethyl benzoylacetate 3 (12 g, 83 mmol) The reaction rnodure was heated on a
steam bath for 20 h, conc HCI (1 mL) was added and heating was contln.led for another 24 h
The cooled mixture was poured Into water (20O mL) and after a few days the product was filtered
and washed wth 50% EtOH to give 5 85 g (30%) of 4, mp 165-185 5°C (EtOH)

34 Name and Unnamed Reactions Name and Unnamed Reacnons 35
BIRCH . HOCKEL . BENKESER Reduction
Reduction of aromatics, unsaturated ketones conlugated dlenes by alkali metals in ,quid
ammonia or amines
1 2 (85%)
3 4 8o 2o 5
1 Huckel W LlebgsAnn 1939 540 156
2 Birch A I J Chem Soc 1944 430
3 Benkeser, R A J Am Chem Soc 1961 77 3230
4 Benkeser RA J Org Chem 1964 29 955
5 Moody, CJ TetrahedronLett 1986 27 5253
6 Webster FX Synthesis 19 87 923
5,8-Dlhydro-l.naphthol (2).2 To 1 naphthol 1 (10 0 g, 0 069 tool) was added
powdered NaNH2, (2 7 g, 0 069 mol), hquld NH3 (100 mL), tea BuOH (12 5 g) and then Na
(3 2 g, 0 139 at) In small pieces AJter evaporation of the NH3, the residue was extracted with
Et20 The od that separated on acidifcatlon solidified and after recrystalllzaton from
petroleum ether (80 100"C) gave 89 5 g of 2 (85%), mp 71 74"C
'9'10-Octalln and ,l,9..octalln (4) and (5) 4 A mixture of 3 (25 6 g, 0 2 tool), and
Et2NH (250 mL) was treated with small pieces of LI (11 55 g 1 65 atoms) After 14 h and
solvent evaporation the residue was treated with water (caution) The mixture was extracted
with Et20 the extract washed dried and distilled to give 19 20 g of 4 and 5 (75 80%). bp 72
77°C (14 mm) 80 20 by GC (Apmzon L 148 °)
B I S C H L E R Benzotnazne synthesis
Benzotnazlne syntheszs from o-nltrophenylhydrazlnes
O=N"NO=  O=N NO "''--'HwN
1 2 (83"/,) 3
1 Bschler A Chem Bet 1899 22 2801
2 Abramovdz, A J Chem Soc 19 55 2326
3 Ramesh, D Synth Commun 1986 16 1525
B I S C H L E R - M O H L A U Indole synthesis
Indole synthesis from ўx amlnoacetophenones
EtOH . 2h
H 2 (11%)
0
1 Mohlau E Chem Bet 1881 14 171
2 Bschler A Chem Bet 1892 25 2860
3 Nelson. L R JAm Chem Soc 1958 80 5957
4 Buu Ho, N P J Chem Soc (C) 1971 2606
5 Bigot P J Chem Soc Perkln Tr 1972 2573

36 Name and Unnamed Reacnons
Name and Unnamed Reacnons 37
B I S C H L E R - N A P I E R A L S K I Isoqulnohne synthesis
Isoqulnoime synthesis from amides of phenethylamlnes
Xylene 2 (31%) 
1 Bischier, A, Naperalskl B Chem Bet 1893 26 1903
2 Morrison, CG J Org Chem 1964 29 2771
3 Ramesh, D Synth Commun 1986 16 1523
4 Thygarayan, BS Chem Rev 1954 54 1033
5 Fodor, G Angew Chem IntEd 1972 11 919
6 Govlndachan TR Org React 1951 6 74
2,3,4,6,7,12"Hexahydrolndolo[2,3a]q,.inollzlne.4.one (2) 2 To stirred 1 (3 0 g
11 8 retool) =n boiling xylene (410 mL), was added P205 (3 15 g) at 45 rnm Intervals The cooled,
filtered solid was added to *ce water (1.000 mL), made bas,c wdh 40% KOH and extracted with
CH2CI2 Evaporation and crystalhzahon from EtOH gave 0 94 g of 2 (31%), mp 234 235aC
B L A N C Cyciizahon
Formabon of cyclopentanones by Cycllzahon-decarboxylatlon of adlplc acids
qCOH
co [=o
300" (30 mln)
1 2 (69%)
1 Blanc, G CR 1907 144 1356
2 Bachmann, N J Am Chem Soc 1949 71 3540
B L A N C - Q U E L L E T Chloroalkylaton
Lewis acid catalyzed aromatic chloromethyiaton (Blanc) chloroalkylaton ((Xlellet)
1 Grassl G,Masselk, C Gazz Churn Ital 1898 28 477
2 Banc G Bu(/ Soc Chum Fr 1 9 23 33 3t3
3 TashlroMasashl J Org Chem 1978 43 1413
4 Fuson R Org React 19 4 2 I 63
5 Quellet R CR 1932 195 155
6 Quellet R Bull Soc Chum Fr 1940 7 196
7 Neda, V J Soc Chem Ind Jpn 1944 47 565
2,2 .Dlchloromethyl.4,4'.dltert-butyldlphenytmethane (3) 3 To cooled (5°C) 1 (35
g 125 mmol) and chloromethyl methyl ether 2 (80 5 g tOO mmol) m CS2 (150 ML) was added
TICI4 (20 mL) The mixture was stirred for t h poured into ice water (3O0 mL) and the organic
layer extracted wdh Phil Evaporation gave 36 g of 3 (76%), mp 90 91°C (EtOH)
p-Methoxyvtnylbenzene (7) 6 4 (125 g 1 25 tool) 5 (44 g 1 mol), 16% HCI (50 mL), and
ZnCI2 (25 g) In petroleum ether (150 mL) was saturated with HCI gas at 5°C After 1 h the
mixture was poured on ice the organic layer concentrated and the reszdue (6) was heated with
two volu rues of pyndlne for 10 h at t t5°C Dlsbllatzon gave 56 70 g of 7 (35 40%), bp 95 96°C
(16 ram)

38 Name and Unnamed Reactwns Name and Unnamed Reactions 39
B L U M Azlndine synthesls
Synthesis of azlndines from epoxides vla amino alcohols or azidd alcohols and reaction wlth
phosphines or phosphites
1 Blum. J J. Org Chem. 1978 43 397, 4273
2 Shudo, K Chem. PharrnBull 1976 24 1013
Threo-2-Azldo-l,2-dlphenylethanol (2).1 A mixture of cis-stllbene oxide 1 (3 92 g,
20 retool) and NaN 3 (4 48 g, 70 mmol) in 50°/. aqueous acetone (60 mL) was refluxed for 311
The solvent was removed in vacuum and the residue extracted with CHCI3 The organў
solution was washed with water, dned (MgSO4) and concentrated. Distillation of the residue
afforded 3 70 g of 2 (77%) as a pale yellow oil, bp 122"C/0 15 mm
Cls-2,3-Olphenylazlrldlne (3). A solution of 2 (0 84 g, 3 5 mmol) and
tnphenylphosphme (0 92 g, 3 5 mmol) n dry Et20 (25 mL) was refiuxed for I h. Et20 (50 mL)
was added and the mixture was allowed to stand ovamlght at 5°C to allow complete
precipitation of tnphenyphosphme oxide. Column chromatography on silica gel yielded 0.53
g of 3 (77%)
B O D R O U X - C H I C H I B A B I N Aldehyde synthesis
Aldehyde synthesis from Gngnard reagents and tnalkyl ortholormate
CsH s- Br  CsH s • MgBr HC(OEt),j 2 CsHs "CH=O
et er reflux, 6h
1 3 (60%)
1 Chlcdoabln AE J Russ Phys Chem Soc 1903 35 1284
CR 1904 138 92
2 Bodroux, F
3 Smdh, L I J Org Chem 19 41 6 437
B O U V E A U L T Aldehyde synthesis
Aldehyde synthesis from Gngnard or LI derivatives with a Iormamle
(65%)
1 Bouveault, L CR 1903 137 987
2 Bouveault, L Bull Soc Chtm Fr 1904 31 1306(3)
1953 75 3697
3 Slce, J J Am Chem Soc
4 Elnchorn, J Tetrahedron Lett 1986 27 179t
5-Methoxy.2.thlenaldehyde (6). 3 5-Methoxy 2 thlenylhthlum prepared from 4 (11 4 g,
01 mol) and LI in Et20 (125 mL) was added slowly to *ce cooled DMF 5 (8 0 mL, 0 11 tool) m
Et20 (75 mL) wdh efficient stlrnn 9 and let stand at 20 ° overnight It was poured into Ice,
extracted with Et2 O and dlstlllallOn gave 9 27 g of 6 (65%), bp 79-81°C, (0 9 ram), mp 24-26°C
from petroleum ether

40 Name and Unnamed Reactions Name and Unnamed Reactions 41
B 0 G E R Heterocycle Synthesis
Hetero Olels-Ak:ler reaction of actNe oleflns (enamlnes) with tdazenes, tetrazenes with loss of N 2
and formation of new N-heterocycles.
1 2 3 (71%)
1 Boger, DL. JoOrg. Chem. 1981 46 2179
2 Boger, DL. J Org Chem. 1982 47 3763
3 Boger, DL J. Org. Chem 1983 48 621
4 Boger, D.L J. Am. Chem Soc. 1985 107 5745
3-Ethyk4-n-propylpyrldlne (3).1 A solution of 4-pyrrolidinohept-3-ene 1 (132 rag, 0.8
retool) in CHCI3 (0 5 mL) was added to a stirred solution of 1,2,4-tdazine 2 (95 rag, 1.2 mmol) in
CHCI3 (0.5 mL) under N 2 at 25°C The resulting dad orange solution was warmed at 45°C for 20
h. Chromatography (SiO2, 50% Et20-hexane) afforded 92 mg of pure 3 (71%)
B O O R D Enol ether synthesis
Synthesis of chloroethers and enol ethers Irom allphatic aldehydes.
Brz
CI.-CHO + HO-Et  CH3_CH.O.Et  CH2.CH.O-Et
1 2 3 Ici Br Br ,r i
 Zn, ,
4 BrMg-CH2"CH'CH = _CH2--CH-O'Et  HzC = CH-CH z-CH=CH-O-Et
CH-CH--ICH BIr 6 (77%) ZnCI2 7 (72%)
1 Boord, CE JAmChemSoc. 1930 52 651
2 Boord, C E J Am Chem Soc 1 9 31 53 1505
3 Boord, CE J Am Chem Soc 1933 55 3293
4 Cromble, L Quart Rev (London) 1 9 52 6 131
1-Ethoxypenta-l,4-dlene (7). 3 A mixture of paraldehyde 1 (20 0 g, 0.45 tool) and anh
EtOH 1 (20 g, 0 43 mol) cooled to -5°C, was saturated with dry HCI gas After al0soqtlon of 20 g
HCI a flow of dry N 2 was passed through The organic layer was separated and dried (CaCI2)to
give 41-42 g ol 3 (87-92%) Ice-coofed 3 (42 5 g, 0 4 tool) was treated with bromine (62 5 g,
0 4 mol) under stlmng Alter 6 h dry N 2 was bubbled through the solution, then the mixture was
dned (CaSC4) There was obtained 60-66 g of 4 (66-73%), bp 73-75°C ( 2 ram), n) 5 = 1 5017
To a Gngnard solution obtained from allyl bromide (40 g, 0 33 mol) and Mg (19 5 g) in Et20
mL), was added 4 (58 g, 0 25 moi) =n Et2C (60 mL) The mixture was poured into AcCH and
after distillation there was obtained, 37-39 g of 6 (77-82%), bp 72-75°C (21 ram)
A mixture of 6 (38 g. 0 2 mol), Zn (55 g, 0 85 at) and ZnC 2 (0 2 g) in BuOH (50 mL) was heated
until 7 distilled out. There was obtained 9 5-10 g ol 7 (72-76%), n) 5 = 1 3887

42 Name and Unnamed Reacnons Name and Unnamed Reacnons 43
B O R C H Reduchon
Reductwe amlnaton of aldehydes or ketones by cyanoborohydnde (or tnacatoxyborohydrlde)6
amon Selective reduction of carbonyls to alcohol, oxlmes to N alkylhydroxylanes, enamlnes
to amines
CCH (CHz)3.CH O + CH3-NH 2 NaSH3CN 
 N--ў
1 2 "-" 3 (43%)
• , ,
O 4 NH 2 5
I Borch, RF JAm Chem Soc 1969 91 3996
2 Borch, R F J Am Chem Soc 19 71 93 2897
3 Borch, R F J Chem Soc Perkln / 1 984 717
4 Lane, C F Synthesis 1 975 135
5 Hutchlns RO Org Prep Proc /nt 1979 11 20
6 Abdel Magld Tetrahedron Lett 1990 31 5595
M-Methylplperldlne (3).2 To the gluteraldehyde 1 blsulflte addition product (3 08 g, 10
mrnol) and 2 HCI (I 3 g, 20 mmol) in MeOH (50 mL) was added NaBH3CN (500 rag. 9 mnlol)
After 48 h at 25"C it was acidified to pHI2, evaporated and the residue dissolved in water and
baslfled with 6 N KOH Alter extraction with Et20 (8x25 rnL). drying (MgSO4) and evaporation
the residue in EtOH (3 mL) was treated with pnc acid (10 mmol) in EtOH to give 1 38 g of 3
pcrate (43%) mp 147 t49°C
Phenylalanlne (5) 4 (186 rag. 1 retool), NH4Br (500 rag, 5 retool) and L=BH3CN (100 mg, 2
mmol) in MeOH (20 mL) was stirred for 48 h at 25°C. treated wdh 36% HCI (5 mL) and after 1 h
evaporated in vacuum The residue in 3 mL of water was passed through Dowex 50 (H + form)
100 mequlv capacdy Washing (water) and eluton with 1 N NH4OH afforded 81 mg of 5 (49%)
B O R S C H E - B E E C H Aromatic Aldehyde Synthesis
Synthesis of aromatic aldehydes and of alk3/I aryl ketones hom aldoxlmes or semmadoazones and
aromatic diazomum salts
(4%)
2 1 3
o
NHz /
j HNO2 Me CH = NCH
 (36%)
1 Borsche, C Chem Ber 1907 40 737
2 Beech, WF J Chem Soc 1954 1297
3 Woodward, R B Tetrahedron 19 5 8 2 1
I/rldlne-:3-aldehyde (3). 2 A solution of 3-am=nopyddlne 2 (23 5 g, 0 24 tool), 36% HCI (68
mL). NaNO2 (17 5 g, 0 25 mol) and water (75 mL) was made neutral (NaOAc) and treated Wdll
lormaldoxlme 1 The rnlure was made aod Coil-3) aJ'K:l after FeCI3 (150 g) was added, t was
boiled for I h Usual work up gave 3 6 g of 3 (14%), 10p 95-100"C416 mm p-Chldroaceto-
phenone was prepared in the same manner from p-chloroandine and acetaldoxlme in 36%

44 Name and Unnamed Reacnons Name and Unnamed Reactions 45
BOUVEAULT. BLANC Reduction
Reduction of esters to alcohols by means of sodium in alcohol
 EIOH -- O
1 2 (2O%) 2 O
1 Bouveault, L,Blanc G CR 1903 136 1676
2 Paquette LA J Org Chem 1962 27 2274
3 Ruhlmann K Synthesis 1 9 7 2 236
4 Chaussar J Tetrahedron Lett 1 9 8 7 28 1173
BOUVEAULT . HANSLEY- PRELOG . STOLL Acyloln
synthes|s
Condensation of two esters to an  hydroxyketone by means of rapidly stirred (8000 rpm) Na
suspension in boiling toluene or xylene
O
,,,.,,,-,,cOOCH  OH
1 (02 mol)
2 (75%)
1 BouveaultL CR 1905 140 1593
2 Hansley VL US Pat 2228258CA 1941 35 2354
3 Prelog V HelvChmActa 1947 30 1741
4 StolI, M HelvChtmActa 1947 30 1815
5 Cramm, DJ J Am Chem Soc 1954 76 2743
6 Finley, K T Chem Rev 1964 64 573
B O U V E A U L T - L O C Q U I N Amlnoacld synthesis
Synthesis of amlnoaclds from malonste esters by nltrosatlon
1 EtONa Ce Hs.CH2 i.Et
Cell s CH 2 - CH (C-OOEt)2 + EtO- N
ZH + NOH
1 2 3 (97%)
C..'I, CH z ! C)(3e Rney N, CsH s CH H COOEr
OH I' NH2
3 4 (%)
1 Bouveault, L,/ocquln, R CR 1902 135 179
2 Hauser, CR JAm ChemSoc 1947 69 1387
Phenylalanlne ethyl ester (4)2 a) Ethyl .Oxlmlno..phenylproplonate (3). A
solution of dlethyl benzylmalonate 1 (50 0 g, 0 2 mol) n EtoH (92 mL) was treated wdh I::tONa
(13 6 g, 0 2 reel) and ethyl n4nte 2 (22 5 g 0 3 rnol) at 0°C The reaction re was kept at -
20°C Ior 20 h Nter evaporation of the solvent under vacuum (no heating), cold ўonў HCI was
added to bnng the pH to 5 Extraction wth I::t20 and evaporation of the solvent gave 40 g of 3
(97%), m 54 57C (rnp 56-57°C from ligrmn, bp 90 120°C)
A solution of 3 (16 8 g, 8O mmel) in EtOH (850 mL) and Raney nckel was hydrogenated at 7O-
75C Removal of the catalyst by filtration and evaporation of the solvent gave 8 3 g of 4 (53%),
I 141 142oc (10

46 Name and Unnamed Reactions Name and Unnamed Reacnons 47
B O Y L A N O - S I M S o-Hydroxyandlne Synthesis
Oxidation ol anilines with persulfates to o-ammophenols.
Me.N.Me Me.N.Me Me.N.Me
[ K,.S,O, = r?-,--L. -.°s°K(H)
[ COflC. HCI - OH
1 2 (40%) 3 (83%)
I Boyland, E, Sims, P J. Chem Soc 1953 3623
2 Behrman, E.J Org. React 1 9 8 8 35 432
o-Dlmathylamlnophenol (3).1 To dimethylanlline 1 (5 0 g, 41 mmol) in water (250 mL),
acetone (400 mL) and 2N KOH (30 mL) was added K2S208 (11.2 g, 41 mmol) as a saturated
aqueous solution at 20°C over 8 h wzth stlmng The solution was evaporated to 250 mL,
washed wdh Et20 (3xl 50 mL), evaporated to dryness under reduced pressure, and the
residue extracted with hot 95% EtOH (3x50 mL) The combined extracts were diluted with Et20
(1500 mL) to gve o-dlmethylammophenyl potassium sulfate 2 (4 2 g) (40%).
The potassium salt 2 (0.46 g) in water (2 mL) was treated with HCI (2 mL) to afford o-
dlmethylamlnophenyl hydrogen sulfate 2 (310 rag, 82%), mp 217-218°C (EtOH)
Heating of 2 (0 4 g, 2 mmol) in conc HCI (5 mL) for 1 h, and partial neutralization of the
cooled solution wdh 2N N=OH, gave 210 mg of 3 (83%), mp 44-45°C (from aq EtOH).
v o n B R A U N Amine degradation
Degradation of tertiary amines to secondary amines with cyanogen bromide (BCN).
55 o reflux
Me H
,
I v. Braun, J Chem. Ber 1907 40 3914
2 Eiderfield, R.C. J Am. Chem. S<x: 1 950 72 1334
3 Wolf, V. LJelgsAnn 1957610 67
4 Boekelheide, V. J Am. Chem. Soc. 1955 77 4079
5 Rapoport, H. J. Am. Chem. Soc 1967 89 1942
6 Fodor, G Can. J Chem. 1969 47 4393
7 Hageman, H A. Org. Feact. 1953 7 198
4-Plpecoltne (3).2 To a solution of BrCN (48 g, 0 46 tool) in Phil (100 mL) was added t-
Isopropyl-4-pipecohne 1 (58 g, 0 41 mol) in Phil (275 mL) over 1 h at 40°C. The mixture was
heated for 45 min at 55-60 ° C and was mmntalned at 20 ° for 36 h. The basic matenal was
extracted with HCI (100 mL) and the solvent dlstdled to give 44 g ol residue. The neutral
Product was refluxed with 48% HBr (300 mL) for 10 h. After distdlation of HBr, the residue was
leaChed in a mixture of EtOAc EtOH (80 20). Filtration of insoluble NH4Br and concentration
gave 3, mp 171-173"C

48 Name and Unnamed Reactions Name and Unnamed Reactions 49
B R E D E R E C K Imidazole synthesis
Synthesis of imldazoles from formamide (acetamtde) and z-dlketones, -ketols, -
aminoketones, -oximlnoketones
CHC-C-CH + H(X)N tSO-C HC --Cc-CH3
.... '..,
o N \C"
3
(so-,,.)
(CH z + HCOkH z  (
H
Ph
I10 2)EtCO=K ii I z (NH4}2 CO NyNH
O O-C-Et Et (7o%)
I Bredereck, H. Chem. Ber 1953 86 88
2 Gnmmett, V. Adv. Heteroc. Chem 1970 12 113
3 Bredereck, H. Angew Chem 1959 71 753
4 Schubert, H. Z. Chem. 1 967 7 461
5 Novelli, A. Tetrahedron Left 1 967 265
4,5-Dlmethyllmldazole (3). 1 A mixture of acetoln 1 (10 g, 0 116 mol) and formamlde 2
(50 mL, 66.7 g, 1 5 mol) was heated for 4 h, distilled in vacuum and the Iracton with lop
165-175"C/11 mm was collected There was obta=ned 6 g of 3 (50%) as an oil which
crystallized, mp 117°C, 3 hydrochicnde, mp 305°C
B R O O K Silaketone reaangement
Reaangement of sila ketone$ to sllyl ethers (w=th chlrallty transfer).
I
1 o OEt OEt OEt 2 (74%)
0
Np...l - .- Mo tBuO- S- O- C.-
1 Brook, AG. J. Org. Chem 1962 27 2311
2 Brook, A.G. Acc. Chem. Res. 1 974 7 77
3 Wilson, S.R. J. Org. Chem. 1981 47 747
4 Kuwalima, J TetrahedronLett 1980 21 623
Benzhydryloxy ethoxy dlphenyl sllane (2). 2 To a solution of benzoyl tfiphenylsllane 1
(2.5 g, 6 9 mmol) in benzene (25 mL) was added a solution of sodium ethoxide In ethanol (2
mL, 0 8 mmol). The solution changed colour and after 11 rain laded almost completely. The
solution was washed with water and the solvent removed in vacuum. The oily residue was
dissolved in hot ethanol (15 mL) and cooled to give 2 (21 g, 74%), mp 67-75°C
Recrystalllzatlon from ethanol gave 1 8 g (64%), mp 77-78,C

50 Name and Unnamed Reactions Name and Unnamed Reactions 51
B R O W N Stereoselectlve reduction
Stereoselective reduction of ketones to alcohols by means of borohydnde reagents
(LI s-Bu3BH or t-BuCIBR* for formation ol chlral alcohols)
OH
5 S (70-90"/. ee)
1970 92 709
1972 94 1750
1972 868
1972 94 7159
1989 54 4504
Cis-,4-tert-butylcyclohexanol (2). 4 To 1 0 M lithium tnmethoxyalumlmum hydnde (LTMA)
(5 0 mL) in THF under N2, was added sec-butylt:rane (from 2obutene and diborane) 1 25 mL,
5 mmol) After 30 rain the mixture was cooled to -78"C and 1 (390 rag, 2 5 mmol) was added
After 3 h, hydrolysis and oxidation (H202) gave 2 (96 5% ClS and 3 5% trans)
(S)-Cyclohexylethanol (6). 5 To 5 5 mmol of 4 in THF (from LI-tBuBH3, HCI followed by
(-)-2-ethylapoplnene 3 D=-42 78 o) was added 5 (0 64 g, 5 mmol) under N 2 After 2 days the
solvent was removed, the residue dissolved in Et20 (20 mL), dlethanolamlne (2 2 equw) was
added and silted for 2 h After fiitratlon and washing with pentane, the filtrates were concen-
trated and chromatography gave 0 42 g of 6 (65%), 90% ee
B R O W N Hydroboratlon
Hydroboration - regloseleCtlve and stereoselectlve (syn) addition of BH 3 (RBH 2, R2BH) to
olefins. Synthesis of alcohol including optically active alcohols from oleflns. Also useful in
synthesis of ketones by "stitching" ol olefins and CO
1 2 3 (100%)
4 S 6
.OH
1 Brown, HC JAm Chem. Sc. 1956 78 2583
2 Brown, HC. J Org Chem 1978 43 4395
3 Masamune, S J Am. Chem Soc. 1986 108 7401
4 Hoffmann, RW Angew Chem. Int Ed. 1982 21 555
5 Brown, H.C. J. Am. Chem. Sc. 1986 108 2049
6 Srebnik, M. AldnchlmcaActa 1987 20 9
7 Brown, H.C J. Org. Chem. 1 989 54 4504

53
52 Name and Unnamed Reacnons Name and Unnamed Reacnons
Isoplnocampheol (6) 2 To a hot solution ol borane methyl sulfide 1 (2 0 mL, 20 0 mmol)
in Et2C (11 3 mL) was added (+)  plnene 2 (7 36 mL, 46 0 mmol), which led to quantitative
formation of 3 After addition of TMEDA 1 51 mL, 10 mmol), reflux was continued for 30 rain
The adduct was filtered and washed with pentane to give 3 32 g of 4 (80%), mp 140-141"C
(Et2C)) A solution of 4 (3 32 g, 8 mmol) In THF (16 mL) was treated with BF3 Et20 (1 97 mL,
16 rnmol) After 1 h, the solid TMEDA.2BF3 was removed and the solution of 5 was oxidized
with alkaline H202 to give 6 (100%)
(.) 3-Hydroxytetrahydrofuran (8] 5 To a suspension of ( ) Ipc2BH (dnsopnocamphenyl
borane 3 (71 g, 25 mmol) In THF, see al:ove at 25°C was added 2,3 -dlhydrofuran 7 (1 9
mL 25 mmol) The reaction mixture was stirred at the same temperature lot 6 h The solid 3
disappeared and formation of trlalkyl l:orane was complete The mixture was brought to 0*C
and acetaldehyde (5 6 mL 100 mmol) was added dropwlse and stlrnng was cont|nued for
another 6 h at 25oC Excess acetaidehyde was removed under vacuum (25°C, 12 mm Hg),
and 20 mL of THF was added The boronate thus obtained was oxidized with 25 mL of 3N
NaCH and 3 75 mL of 30% H202, and maintained for 5 h at 25°C The aqueous layer was
saturated with K2CC 3, extracted with 3 25 mL Et2C and the organic layer dried (MgSC4) The
solvent was evaporated the residue filtered through silica pentane eluent removed 
plnene whereas the Et2C eluent afforded the alcohol 8 which on distillation yleided 1 87 g
bp 80°C/15 mm (92%) GC purity 99%, D = 17 3 o (c 2 4 MeOH 100% ee)
B R U Y L A N T S Amlnation
Amination alkytation ol aldehydes via -cyanoamines
© .
1 2 3 (e2 °/.)
H
3 + C.gSr
4 5 (78%)
1 Bmylant P Bull Soc Chum Beige 1924 33 467
2 Bmylant P Bull Soc Chtm Beige 1 9 2 6 35 139
3 Bersoh HW Arch Pharm 1978 311 1029
4 Ahlbrecht, H Synthests 1 985 743
N-(4-hex-2-ene)-pyrrolldlne (5) 3 Pyrrolldlne 2 (0 71 g 0 1 tool) is neutralized by 4N HCI
and mined with a solution of KCN (6 5 g 0 1 tool) in H20 (50 mL) The mixture IS added siowly to
a stln'ed solution of crotonaldehyde 1 (7 0 g 0 1 tool) in Et20 (100 mL) at 0*C The mixture is
stined lot 3 h at 20 ° The water layer is separated, washed with Et20 (4 x 30 mL), the combined
EI20 layers washed (H2C), tined (Na2SO4) and evaporated The residue is distilled to yield
12 38 g of 3 (82%), 10p 51"C (I 5 10 2 torr)
To a stlned solution of 3 (10 57 g 70 mmol) in THF (20 mL) under Ar a solution of EtMgBr (1
molar 22 mmoi) in THF is added slowly at 0°C The resulting mixture is stlwed Ior3 h at 20 o,
then diluted with Et20 (50 rnL) The mixture is washed with water, the solvent removed and the
rsldue dlstdled to give 8 35 g of 5 (78%), bp 830C (19 ram)

55
Name and Unnamed Reacnons
Name and Unnamed Reacnons
B U C H E R E R - L E P E T I T Naphthol (Naphthyiamlne) Synthesis
Synthesis of naphthylam=nes from naphthols and naphthois from naphthylammes
CH CH
 200"C
1 2 (93%)
NaHSO3
1 Le Petd R Bull Soc Ind Mulhouse 19 0 3 73 326
2 Bucherer H T J Prakt Chem 19 0 4 69 49(2)
3 Johnson W S J Am Chem Soc 1 944 66 210
4 Seeboth H Angew Chem 1958 70 312
5 Drake NL rg React 1942 1 105
6 We,don B C L Quart Rev 19 52 6 380
1-Methyl-2-naphthylamlne (2) 3 A mixture of 1 methyl 2 naphthol 1 (7 8 g, 50 mmo0
NaHSO3 (10 g 0 1 mol) 28% NH4OH (40 mL) and water (10 mL) was heated to 200 205°C for 48
h The coled solulion was made alkahnewlth NaOH solution and extracted with Et20 The dned
ether solution was treated with HCI gas to afford 2 hydrochlonde which was filtered treated wdh
alkah and extracted with EI20 Evaporation of the solvent gave 7 2 g of 2 (93%), mp 46 50°C
Recrstalhzed from petroleum ether (lop 60 70°C) mp 49 50°C
BUCHNER - CURTIUS -
S C H L O T T E R B E C K Homologahon
Ring enlargement of benzene denvatrves by carbenes generated from dlazo compounds (better
=n the presence of a Rh catalyst) Conversion of aldehydes to ketones by dlazo compounds
(Schlotterbeck) see also Pfau Platter
(CtNO2}2CsHCOO)4Rh2
2 3 (85%)
' CH 
CHO 12d
4 6 (7o%) °
1 Buchner E Cudlus T Chem Bet 1885 18 2371
2 Buchner, E Chem Bet 1896 29 106
3 Schotterbeck, F Chem Bet 1907 40 479
1950 72 2337
4 Ramonczay J J Am Chem Soc
J Am Chem Soc 1957 79 352
5 Doenng W v
6 Anclaux A J J Org Chem 19 81 46 873
S T
Tetrakls(2,4.dlchloro.3,5.dlnltrobenzoato)dlrhodlum (It) (2) o a solutlon of
RhCI3 3H20 (250 rng 10 mmol) and 2 4 dlchloro 3 5 dlndrobenzoio ac (3 g 10retool) m EtOH
(tO0 mL) NaHCO3 (220 rng) was added and the mdure was refluxed under N2 Cold filtration
afforded 2 as a green soll after washing wdh Me2C( and Et2 O In 69% yield
loCarboxymethyl-2,4,6ocycloheptatrlene (3) 6 Methyl dlazoacetate 1 (0 5 g 5 mmol)
was added to Phil (8 4 g 100 mmol) and catalyst 2 (0 02 mmol) over 2 h while the mture was
stnTed at 20°C till the 2175 cm 1 band disappeared The mixture was distilled under vacuum to
afford 0 58 g of 3 (85%)

56 Name and Unnamed Reactions Name and Unnamed Reactions 57
B U R G E S S Dehydration reagent
Thermolysls of tedlary and secondary alcohols wtth (carbomethoxysulfamoyl) tdethylammonlum
Inner salt 5 to give oleflns; also conversion of amides to nltdles
OCN- SO2Ct ч MeOH  M3= C-N- SO-zCI + NEj  MeO 2 C-- SO2EI:
1 2 3 4 5
6 55' 7 169%)
1 Burgess, EM. J. Org. Chem 1973 38 26
20'Grodnlck, J.S J. Org. Chem. 1974 39 2124
3 Goldsmith, D.J. Tetrahedron Lett. 1 980 21 3543
4 Claremon, DA. TetrahedronLett 1988 29 2155
5 Burgess, E.M. Org. Synth. 1 977 56 40
Inner Salt (5). t Anhydrous MeOH 2 (18 8 g, 0 55 mol) 1 Phil (25 mL) was added over 30
min to 1 (65 72 g, 0 5 mol) In Phil (200 mL) with cooling. The solvent was removed In vacuum
and the residue recrystalllzed from PhMe to give 61 0 g of 3 (91.9%), mp 70-71°C. 3 (3.47 g,
20 mmol) in Phil (50 mL) was added dropwse to Et3N (4 6 g, 45 mmoi) in Phil (25 mL). EI3N
.HCI was filtered, the filtrate evaporated and the residue crystallized from PhMe to give 3 87 g of
5 (81%), mp 71-72°C.
3,4.Epoxy.2.methylbut-l,ene (7). 1 3,4-Epoxy-2-methylbutan-2-ol 8 (3 g, 29 mmol) was
added neat to 5 (9 5 g, 40 mmol) at Z0°C under N2 The mixture was warmed to 55°C and 1 41 g
of 7 (69%) distilled.
B U R T O N Trifiuoromethytaton
Tnfluoromethylation of aryl iodides wdh Cd (Cu) reagents
DMF
C 2 -CCBr + Cd --.- CFs-Cd ч CdBr;z
t
Cu Br, 0 o "
NOz NOz
a 4
1 Budon, D.J J Am Chem Soc 1985 107 5014
2 Budon, D J J Am Chem Soc 1986 108 832
3 Ctark, JH J Chem Soc Chem Commun 1988 638
Tnfluoromethyl Cd chloride (2). 1 To actNated Cd (22 4 g, 0 2 at) In DMF (50 mL) was
condensed F2C ClBr 1 (8 6 mL, 0 1 mol) After an exotherm reaction a precipitate formed.
After 2 h stimng at 25 o, the brown solution was filtered under nitrogen and the precipitate was
washed wtth 10-15 mL of DMF The soluhon of 2 (1 M) thus obtained was utilized in the next
react.l.
pTrlfluoromethylnitrobenzene (4) To a solution of 2 (0 1 mol) and CuBr (7 17 g, 0 05 mol),
was added at 0°C a solution of p-K)dontrobenzene 3 (8 71 g, 0 O35 mol) The mixture was
heated for 4-6 h at 60-70°C and steam distilled Exlraction of the organio layer and
redmtillation gave 3 93 g of 4 (75%)

Name and Unnamed Reacnons 59
Name and Unnamed Reactions
C A N N I Z Z A R O Oxidation - Reduction
A redox reaction between two aromatic aldehydes (or an aromatic aldehyde and
formaldehyde) to a mixture of alcohol and acid
 Co2 H 00HMe
3m/o NaOH
PhCH=O + CHO  PCH= OH + HCO9t
1 Whler, F Ann 1832 3 252
2 Cannlzzaro, S Ann 1853 88 129
3 Bruce, R A Org Prep Proced Int 1 9 8 7 19
4 Geissmann, T A Org React 19 44 2 95
o.Methoxybenzyl alcohol (2) and o.Metllyloxybenzolc acid (3)3 To a solution of
KOH (120 g, 2 mol) In water are added o methyoxybenzaldehyde 1 (136 g, 1 mol) under
efficient stimng and external cooling with water Stlmng was maintained until a stable
emulsion was obtained After 24 h at 30°C, the mixture was diluted with water and extracted
with Et20 Evaporation of the solvent and vacuum distillation of the residue afforded 55 g of
2 (79%), bp 245-255°C Acidification of the aqueous solution, extraction with Et20 and
distillation of the solvent gave 3, mp 98 100°C
C A R R O L L Allylation
Carboxylation and subsequent allylation of alkyl hetemcycles (via Clalsen rearrangement of allyl
esters)
oH
c---:
   2 PhO- ;CI2
1 2 (99%) O
HC.,.( CH3 , 2OmC H3C. N..,CH=
4 (33%) 5 (30%)
t Carroll MF J Chem Soc 1940 704
2 Klmel, W J Org Chem 1958 23 153
3 Stephen W J Org Chem 1984 49 722
4 Pedraza KF J Heterocycl Chem 1986 23 581
2.(3-Pentenyl)o3,5,6-trlmethylpyrazlne (5) 4 To LDA (from IPr2NH (7 8 g, 77 7 mmol)
in Et20 and 1 6 M nBuLi (43 6 mL 77 2 mmol) in hexane was added 2 3 5 6
tetramethylpyrazme 1 (10 g, 73 5 mmol) In Et20 (100 mL) After 30 mln at 0°C dry CO2 was
passed through for 30 mln Filtration, washing (Et20) and drying gave 13 5 g of 2 (99%)
To 2 (1 g 5 4 mmol) in dlmethoxyethane (25 mL) was added sequentially pyndlne (0 85 g, 10
mmol), phenyl dichlorophosphate (1 71 g 8 1 mmol) and 3 butene 2-ol 3 (9 78 g, 10 8 mmol)
Alter 18 h al rt the mixture was poured =nto ice water and extracted with CHCI3 Purification by
HPLC (50% EtOAc In hexane) yielded 420 mg of 4 (33%)
Heating of 4 (100 rng 0 42 mmol) for 18 h at 200°C yielded 2O 28 mg of 5 (25 35%)

60 Name and Unnamed Reacnons Name and Unnamed Reacnons 61
C H A N Reduction of Acetylenes
Stereospeclflў reduction of acetylenlc alcohols to E- allylio alcohols by means of sodium
bls(2 methoxyethoxy)alumm=um hydride (SMEAH)
Me Me
, o
,
M.; NaAIHOCH2CI..12OCH,jk H, OH kH l
(SMEAH) Me -
heat
1 2 183=/,)
1 Chan KaKong J Org Chem 1976 41 62
2 ChanKaKong J Org Chem 1976 41 3497
3 Chan, KaKong J Org Chem 1978 43 3435
(4S,6R)-(-)-(E)-6,10-Dlmethylundec.2-en-4.ol (2) 2 To a solution of (4S 6R) ( )
610-dlmethylundec 2 yn 4-ol 1 (19 9 9 66 mmol) n dry Et2 O (75 mL) was added dropwse
with etlrdng to a 7O% benzene solution o! sodium b=s(2 methoxyethoxy)aiumlnlum hydride (3
mL) In Et20 (60 mL) The resuitlng mixture was sbrred and refiuxed under Ar for 20 h then
cooled in an ice bath and cautiously decomposed by the dropwlse addition of dliute H2SO4
(20 mL) Extraction with Et20 washing with NaHCO3, evaporation of the solvent and
distillation gave 1 619 of 2 (83 8%) as a colorless oft, bp 85C (011 ram) (bath temperature),
[o]2D5 = 9 0°C (c 3 79 CHCI3) no Z somer was detectable
C H A P M A N Rearrangement
O to N aryl migration in O-aryhmlnoethers
Ph CI COOCH o  " "CI
1 2 3 COOCH
I Chapman AW J Chem Sc 1925 127 1992
2 Oauben WG J Am Chem Soc 1950 72 3479
3 Crammer F Angew Chem 1956 68 649
4 Roger R Chem Rev 1969 69 503
5 Schulenberg J W Org React 1 9 65 14 1
N-(4 Methoxyphenyl)-N-benzoyl-3-chloro-3-chloroantranlllc acid (4) 2 To ice
cooled NaOEt (from 0 11 g Na and 10 mL EtOH) was added in rapid succession methyl 2 chlom
6 hydmxybenzoate 2 (0 88 g 4 7 mrnol) and N (4 methoxyphenyl)benzlrndyl chloride 1 (t 14
g 4 7 rnnl) in EI20 (30 mL) The mixture was shrred vigorously and aliowed to stand at i1 for 48
h The oily solid obtained after evaporallon was heated to 210 215°C for 70 mm under N2 The
product was diluted with water (5 4 mL) EtOH (10 8 mL) and treated with 1 M NaOEt (5 4 mL)
The mixture was refluxed for 90 men the solvent evaporated and the aqueous solution aclditled
The dark oll was heated with NaOH (7 5 g) in EtOH (22 mL) After removal of benzoic acid by
exhaustive extraction with water the product was recstalhzed from EtOH to give 0 36 g of 4
(27 7%), mp 139 5 140 5°C

62 Name and Unnamed Reacnons Name and Unnamed Reacnons 63
C H I C H I B A B I N Amlnaticn
ў{ Amlnatton of pyndlnes qulnollnes and olher N heterocycles
1 2 (36%1
H S KMO. .N
Chlchlbabln A
van der Plas H C
Bunnette J F
Rykowscy A
Leffler M T
J Russ Phys Chem Soc 1 91 4 4 6 1216
J Org Chem 1 981 46 2134
Chem Rev 1951 49 375
Synthesis 1 9 8 5 884
Org React 1 9 4 2 1 19
2-Amlno-l,5-Naphthyrldlne (2) 2 To a solution of potassium amlde (from 0 15 g of K) in
IlquK:l ammonia (17 mL) was added 1 5 naphthyndlne 1 (0 2 g 1 5 mmol} After 15 mm stiffing
KMnO4(0 8O g) was added and after another 10 mln (NH4)2SO4 was added to destroy the
KNH 2 The NH 3 was evaporated conc NH4OH was added and the solution was continuously
extracted with CHCI 3 for 48 h The residue obtained alter distillation of the CHCI 3 was purified
by preparative TLC (CHCI 3 EtOH 10 1) to give 80 mg of 2 (36%) mp 238 240°C
C H I C H I B A B I N Pyndlne synthesis
Pyndlne synthesis from aromatic acetaldehydes and ammonia
,CH z CHO EtOH
+ NH 3 
o 
OCH3
'i Ar ] N H _
ArCH EtOH A
H
3 ( 13°/@ )
1 Chich,babln A J Russ Phys Chem Soc 19 0 6 37 1229
2 Ehel EL J Am Chem Soc 1953 75 4291
3 Sprung MM Chem Rev 1940 26 301
4 Frank, R L Org Synth Coil IV 451
5 McGIli C K Adv Heterocycl Chem 1988 44 1
3,S-D,veratrylpyrldlne (3) 2 A solut,on of homoveratric aldehyde 1 (45 5 g, 0 25 mol} ,n anh
EtOH (250 mL) was refiuxed for 1 h under a flow of dry NH3 2 The solvent was removed and
the residue was heated wth 1N HCI in EtOH (100 mL) The HCl and EtOH were removed n
vacuum and the resK:lue was slurned in acetone The hydrochlonde of 3 was filleted,
dLolved in 98% EIOH (350 mL) at reflux and retreated with 25% NH4OH (100 mL) On
Cool=rig the base separated It was filtered and dried to afford 5 66 g of 3 (12 9%)
Recn/stalllzatlon gave 4 41 g mp 170 173°C

64 Name and Unnamed Reacnons Name and Unnamed Reacnons 65
C f A M I C I A N Photocoupllng
Reductlve coupling of ketones to dlols
hv
1 Cam=canG Chem Ber 1900 33 2911
2 DeMayo P Quart Rev (London) 1961 15 415
3 GOth, H HelvChtmActa 1965 48 1395
C I A M I C I A N - O E N N S T E D T Cyclopropanation
Cyciopropanatlon of alkenes w=th diohiomcafloene derived from CHCI 3 and sometimes
subsequent ring enlargement of fused cyciopropanes Cl
2 CHCkj  (10%)
CI
Ph-CH---CH 2 + CHC NaH z,_Phci
3 D|benzo(18)crown 6
1 Clamiclan G Dennstedt N Chem Bet 1881 14 1153
2 Parham WE J Am Chem Soc 1955 77 1177
3 Vogel E Angew Chem 1 9 60 72 8
4 Makosza M Angew Chem Int Ed 1974 13 665
1,1-Dlchloro-2-phenylcyclopropane (4)4 To styrene 3 (10 4 g, 0 1 mol), CHCI3 (11 9
g 0 1 mol) and 50% NaOH, was added dlbenzo(18) crown 6 (0 36 g 1 retool) After a todd
exothermc reaction and work up there was obtained 16 25 g of 4 (87%). bp 112°C/15 ton"
C L A I S E N - G E U T E R - O I E C K M A N N Ester condensation
Synthess of open chain or cyclic  keloesters by aldol type condensation
NaOMe
1 2175%)
Cot C-°tBu Nail
B heat
-- u
 3 %)
1 Geuter A Arch Pharm 1863 106 97
2 Clalsen, L Chem Ber 18 87 20 651
3 Dleckmann W Chem Ber 1894 27 965
J Org Chem 19 73 38 1425
4 Cohen, H
5 Taylor R J K Synthesis 1 9 8 3 996
6 Tanabe J Chem Left 1986 1813
1954 54 1029
7 Thyagaralan0 B S Chem Rev
8 Schaefer J P Org React 1967 15 1
2ot-Butoxycarbonylcyclopentanone (4) 4 To a stirred suspension of Nail (24 g, 1
rnol) in Phil (400 mL) (N2) was added 3 (5 0 g 20 mmol) and t BuOH (2 0 mL) in one portion
and the mixture was boiled for 30 mm Another porbon of 3 (120 9, 0 465 mol) in Phil (200
mL) was added dropw]se for 45 mm and relkJx was cont=nued for 4 5 h The mixture was
neutra Ized with AcOH, water (750 mL) was added followed by extraction Et20 (2x500 mL)
Evaporation of Ihe solvent and vacuum distillation afforded 65 5 g of 4 (73%), bp 80 85°C (2
ton), Rf 0 25 silica gel EI20 hexane 1 2

66 Name and Unnamed Reacttons Name and Unnamed Reactions 67
C L A I $ E N - I R E L A N D Rearrangment
Rearrangement of allyl phenyl ethers to o (or p-)allylphenols or of allyl v,nyl ethers to Ґ,-
unsaturated aldehydes or ketones (Clalsen) Rearrangement of allyl esters as enolate anions to
Ґ,-unsaturated acids (Ireland)
Me ?H Me
OH
+ CI  NaOM
1 2 3 4(S7°/o) ,,.
,5 0 OLI
Clalsen, L Chem Ber
Rhoades S J J Am Chem Soc
Daub O W J Org Chem
Tarbell D S Org React
Ireland, E J Am Chem Soc
20° CsHll O
OH 6 (83 o',)
99 ';% E
1912 45 3157
1955 73 5060
1986 51 3404
1944 2 1
1972 94 5897
2,6-Dlmethyl-4-(cc-methylallyl)phenol (4) 2 To refluxmg 1 (122 g. 1 mol) In MeOH
containing an equivalent of NaOMe was added 2 (9O 5 g, 1 mol) over 2O mln After 2 h reflux
workup afforded 75 7 g of 3 (43%), bp 55 56°C (0 3 mm) 3 (17 6 g, 0 1 tool) in dlmethylanlllne
was refluxed for 3 h to gve 11 8 g of 4 (67%), bp 89 90°C (0 5 mm)
4-Decenolc acid (6) 5 N Isopropylcyclohexyl amine (1 70 g, 12 1 mmol) in THF (20 mL) at
0°C was treated with BuLl (5 mL, 11 1 retool) in hexane After 10 rain 5 (1 64 g, 10 mmol) was
added dropwlse at 78°C After 5 rain stlrnng the mixture was warmed to 200C poured into 5%
NaOH (20 mL), extracted with Et20 the aqueous solution treated wth HCI, extracted with
CH2CI2 and the solvent evaporated This yelded 1 36 g of 6 (83%), 99 5% E
C L A Y - K I N N E A R - P E R R E N Phosphonyl Chloride Synthesis
Synthesis of alkyl phosphonyl chlorides from alkyl chlorides or from ethers with PCI 3 AICI 3
C2HsC + AICI 3 + PCI 3  C2HsCIAICI3PCI 3  C2HsPCI 2
3 1 2 4 5 (43°°)
(Hs)-zO .1 + 2  5
6
1 Clay JP J Org ChPm 1951 16 892
2 Klnnear, M M Perren E A J Chem Soc 19 5 2 3434
3 Hamilton C S Org Synth Coil vol IV 950
Ethylphosphonyl dichloride (5) 1 A From ethyl chloride To cooled st=fred AICI3 1
(13 3 g, 0 1 tool) and PCI3 2 (13 7 g 0 1 tool) was added 3 (19 3 g 0 3 mol) After 2 h stlmng,
Ihe mixture was kept for 24 h at 4°C The cstalhne complex 4 (18 9) was filtered dissolved in
CH2CI2 (200 mL) cooled to 0°C and Ireated with 32=/, HCI (25 3 mL) The mixture was cooled
for another 2 h and hltered The hltrale was concentrated and the res=due d=stdled to give 7 6 g
of 5 (43%) bp 174 5°C
B From dlethyl ether Et20 6 (18 5 g 0 25 tool) was added to a m=xture of 1 (66 5 g, 0 5
tool) and 2 (68 5 g 0 5 mol) at 0°C The mixture was healed for 7 h at 100=C (sealed tube) The
crystalhne product was dissolved n CH2CI 2 and hydrolyzed w=th water After fdlratlon and
distillation 28 g of 5 (43%) was isolated

68 Name and Unnamed Reacnons Name and Unnamed Reacnon 69
C L E M M E N S E N Reduction
Reduction of ketones or aldehydes to hydrocalt)ons by means of zinc amalgam and aczd
HCl reflux
H H
1 2 (go'/.)
1 Clemmensen, E Chem Ber 1913 46 1838
2 Dauben, WG J Am Chem Soc 1954 76 3864
3 Sanda G TetrahedronLett 1983 24 4425
4 Slarschewsky, W Angew Chem 1959 71 726
5 Vedels E O React 1975 22 401
cls-g-Methyldecalln (2). 2 cls 10 Methyl 2 decalone 1 (8 0 g, 48 2 mmol) was heated
under reflux with amalgamated znc (40 g) n AcOH (35 mL) and 32% HCI (17 5 mL) Reflux was
manta=ned for 17 h and evel7 2 h there was added HCI (2 mL) Water (6O mL) was added and
the mixture was steam distilled Neutralization of the distillate with Na2CO3 extraction with
pentane and evaporation of the solvent followed by distillation from potassium afforded 6 57 g
of 2 (90%) bp 91 5 - 92 0°C/20 mm, n2D5 = 1 4791
C L O K E - W I L S O N Cyclopropylketone Rearrangement
Rearrangement of cyclopmpyl ketones or Imines to dlhydmfurans or dlhydropylToles,
thermally, photochemcally, or by LewLS acids
MeO v '1 AlzCJ24h  Me0 ''
+ Et 3 (100%)
M
1 Cloke, JB JAm ChemSoc 1929 51 1174
2 Wilson, CL JAm Chem Soc 1947 69 3002
3 Aionso, ME J Org Chem 1980 45 4532
4 Hudllcky, T Org React 1986 33 247
2,4-Dlmethyl-3-carboxyethyl-5(p-methoxyphenyl)-4,5-dlhydrofu ran (3). 3 A
mixture of syn and anti cyciopropyl- ketoesters 1 and 2 was left in contact with neutral
alumina activity I in CHCI3 for 24 h The starting materials 1 and 2 dlsal0peared and 3,
homogeneous by HPLC and NMR in quantitative yield, was isolated

70 Name and Unnamed Reactions Name and Unnamed Reactiotu "11
C O L L M A N Carbonylatlon Reagent
Oipotassium Iron tetracalbonyl in the synthesis of aldehydes and ketones from alkyl halldes.
K(sec-C=Hs)]BH + Fe(CO)s  K2[Fe(CO)=]
1 2 3 (98%)
3
Br 
4 5 (oo)
OTs
T= -'-'" o
1 Collman, J P Acc, Chem. Res. 1986 1 136
2 Collman, J.P. J. Am. ChemSoc. 1973 95 4089
3 Collman, J P. Acc. Chem. Res. 1975 8 342
4 Collman, J.P. J.Am. Chem. Soc. 1977 99 2515
5 Glalsy, JA. J. Am. Chem Soc 1978 100 2545
6 Glaisy, J.A. J Org Chem 1978 43 2280
Dlpotasslum Iron tetracarbonyl catalySt (3). 6 A THF solution of 0.5 M of K-selectride
(potassium sec butyroorohydride) 1 (70 mL, 35 mmol) was refluxed wdh Fe(CO)5 2 (3 22 g,
15 6 mmol) for 4 h After coohng, the whde solid was filtered (Schtenk technique) and
washed wdh hexane (50 mL) Vacuum drying afforded 4 0 g of 3 (98%), mp 270-273°C (dec)
- Caution The by-product (sec-C4Hg)3B is spontaneously inflammable, the waste solvents
must be treated with a mild oxidizing agent (NaOCI}.
Nonanal (5). Octyl bromide 4 (89.44 rag, 0.46 retool), 3 (94.5 rag, 0.0384 mmol) and Et3P
(132.5 rag, 0 508 mmol) were stirred for 12 h Glacial AcOH (200 mL) and tndecane (100 mL)
(as reference standard} was edded GC analysis indicated 100% yield of 5.
C O M B E S Qulnoline Synthesis
Qulnoline synthesis from anilines and -dlketones
1 2 3 (83%) 4 (96%)
1 Cornbes, A. Bull Soc Chlm Fr 1882 49 89(2)
2 Johnson, W S J Am. Chem Soc 1944 66 210
3 Born, J L J Org Chem. 1972 37 3952
4 Borgstrom, FW Chem Rev. 1944 35 156
5 Smfert, W Angew Chem Int Ed 1962 I 215
4-(2-Naphthyllmlno)pentanone-2 (3). 2 A mlxtura of -naphthylamlne 1 (5 0 g, 0 0346 mol),
acetytacetone 2 (5 85 g, 0 585 tool) and dnerlte (10 g) was heated on a waist bath for 3-4 h
The crude product 7 55 g (96%)° mp 89-96°C, after recrystallizatlon from petroleum ether gave
65 g, of 3 (83%), mp 98-99C
2,4-Dlmethylbenzo(g)qulnollne (4). A mrxture of 3 (13 4 g, 0 059 mol) in HF (300 mL) was
maintained for 24 h at 20°C The residue obtained after removing Ihe HF was neutrahzed wdh
10% K2CO 3 solution, extracted wdh El20 and the solvent was evaporated to yield 11 75 g of
4 (96%), mp 91o92 5°C

72 Name and Unnamed Reacnons Name and Unnamed Reacnons 73
C O N I A Cyclzaton
Thermal cycllzatlon of dlenones enals, ynones, dlones ketoesters, etc, to monocycllc splrocyclic
blcycllc derivatives, (ene reaction of unsalurated enol)
1 2 3 (le%) 4 (loo%)
7 (e%)
CO=El
1 Coma J M Tetrahedron Lett 1965 3305, 3319
2 Cona, JM Bull Soc Chlm Fr 1966 278 281
3 Krapcho, A P Synthess 19 7 4 416
4 Coma J M Angew Chem Int Ed 1978 14 473
2 (Penten-4'-yl) cyclohexanona (3). To 1 (10 9 g 01 mol) and 2 (14 8 g, 0 1 reel) m Phil
(50 mL) was added dropwlse 2N sodium t amytale After 12 h reflux and neutrallza|lon w=th HCI I
organic layer was washed and dned The residue obtained after evaporation of the solvent was
distilled in vacuum to give 3 0 g of 3 (18%), bp 114 116°C (10 rain)
Methyi-l-splro-(4,5)-dacanone,-6 (4) 4 Heahng of 3 at 350°C for 1 h gave 4 as a colorless
In quantitative yield, 4oDNPH (from MeOH), mp 146°C
C O O P E R - F I N K B E I N E R Hydromagneslallon
Ti catalyzed reaction of Grlgnard reagents with oleflns or acetylenes
 CHz CH2OH
1 2) 02 3
C4H C  C S,Me3 l BuMgBr/Cp21CI C4H9
H;C=C. H (>98%Z)
1 Cooper GD Flnkbemer HL J Org Chem 1962 27 3395
2 Sato, F J Chem Soc Chem Comm 1981 718
3 Sate F Tetrahedron Lett 1983 24 1804
J Chem Soc Chem Comm 1983 162
4 Sate F
5 Sate, F Tetrahedron Lett 1984 25 5063
-(&3-Cyclohexenyl) ethanol (3) 1 To Grlgnard reagent 1 prepared from Mg (13 2 g 0 55
at g) and propyl bromide (61 3 g, 0 5 reel) in EI20 (150 mL) was added cooled 2 (54 g. 0 5
reel) followed by TICI4 (1 mL) After 2 h reflux a second portion of TiCI4 (0 45 mL) was added
and reflux was continued for another 14 h The mixture was oxidized with dry air DlStlllallon
ytelded 25 g (40%) of 3 10p 92 94°C
3,.Trlmethylsllyl.2.ethylfuran (6) 5 A catalytic amounl of Cp2TICI2 (0 12 g 0 48 mol) was
added to iBuMgBr in Et20 (43 mL 0 4 M sol 17 mmol) under Ar at 0°C After 5 mn stlmng 4
(0 18 g 6 8 mmol) was added and the mixture was stirred al 25°C for 6 h To this solution was
added proplonitnle (0 48 g 8 8 mmol) The mixture was shrred for 2 h al 25°C quenched with 2
N HCI and extracted with Et20 The extract was tined evaporaled and the residue
chromatographed (silica gel) to afford 0 94 g of 6 (82%)

74 Name and Unnamed Reacion Name and Unnamed Reacffon 75
C O P E Reanangement
3,3-Sigmatropic rearrangement of 1,5-dlenes
= CO2EI 150°
2El NaOEI 
1 2 3 (34%) 4 (68%)
1 Cope, AC. J. Am. ChemSoc 1940 62 441
2 McDowell, DW J Org Chem 1986 51 183
3 Baldwin, JE. J. Org. Chem. 1987 52 676
4 Vogel, E LleblgsAnn 1958 615 I
5 Lutz, R.P Chem. Rev 1984 84 205
6 Bleched, S Synthesis 19 89 71
Ethyl 2-cyano-4-methyl-4-ethyl-hepta.2,8-dtenoate (4). 1 Ethyl 2-cyano-4-methyl-3-
hexenoate I (85 g, 0.5 mot) In EtOH (200 mL), was treated wdh NaOEt (from 12.5 g, 0.5 at Na
in 100 m/EtOH). To the sodium salt of I was added dropwlse under stirnng allyl bromide 2
(66 55 g, 0 55 mol). The mixture was refiuxed until neutral (1 h), and after cooling, water was
added The mixture was extracted with benzene and after solvent evaporation the residue was
distilled n vacuum The first fraction gave 67 g of 3, bp 90-143°C (1 mm) After shaking wth
20% NaHSO3 the product was redistilied through a Widmer column to give 37 g of 3 (34%), bp
94 5-96°C (I ram) 3 (12 g, 55 mnlol) was refluxed for 20 mn and distilled in vacuu to yield 8 g
of 4 (66%), bp 147-148°C (16 ram), n) 0 - 1 4780.
COPE - MAMLOC - WOLFENSTEIN Olefinsynthesls
Olefin formation by ehmlnaton from ted amine N-oxides
1 2 3 19o%)
1 Mamloc, L, Wolfensteln, R. Chem Ber 19 00 33 159
2 Cope, AC TetrahedronLett 1949 71 3929
3 Bluth, M TetrahedronLett 1984 25 2873
Chem Rev 196 0 60 448
4 De Puy, C H
5 F:ujita, J Synthesis 1978 934
6 Org Synth Coil II 381
Cls cyclooctene (3). 2 To ce cooled N,N-dlmathyicyclooctylamlne I (5 0 g. 32 retool) in
MeOH (10 rnL), was added over 30 rain 35% hydrogen peroxide (10 0 g. 99 mmol). Stin'ing
was continued untd the amine had been consumed (24 h) The excess of peroxide was
destroyed by stirnng with plahnum black (0 25 g) for 5 h. The ptahnum was removed by
filtration and the filtrate was concentrated tn vacuo to a syrup (max letup 30-40°C), to give 2.
Amine oxide 2 was heated under vacuum (10 ram) in a N2 atmosphere and the tempemtura
wasralsed 1-2o/mln Decomposlton and distlllahon began at 100°C and ended at13 o°C
1'he dishllate was treated wth HCI, and congelated with dr ice The product which separated
as an oll was distilled to give 3 22 g of 3 (90%), mp -16 °. bp 658C (59 ram) 145-146°C (760
ram), n = 1 4684.

76 Name and Unnamed Reacttons -
Name and Unnamed Reacttons
C 0 R E Y Oxidizing Reagents for Alcohols
Pyrldlnlum chlorochromate 1 or CrO3-dlmethylpyrazole 4 for ox.,datOn of alcohols to ketones
or aldehydes
1 0
3 (3"/o)
S 8 (%)
1 Corey E J Tetrahedron Left 1973 2647
2 Dauben WG J Org Chem 1977 42 682
3 Corey EJ Tetrahedron Left 1979 399
Isophorone (3) 2 To a stuffed slurP/of I (prepared from 8 M HCl. CrO 3 and pyndlne at 00) 1
(4 30 g 20 mmol) in CH2CI 2 (30 mL) was added in one podon a soluhon of 1 5 5
tnmethylcyciohex 2-ene 1-ol 2 (1 40 g 10 mmol) in CH2CI 2 (10 mL) at 20°C After 3 h stlrrlng
the mixture was extracted with EI20 ' the extract was washed with 5% NaOH 5% HCI and
saturated NeHCO 3 After eveporabon of the solvent the product was distilled bulb to bulb to
afford 1 33 g of 3 (92%) bp 213 214°C. n) 0 = 1 4795
Acetophanone (6) 3 5 Dlmethylpyrazole (580 rag. 6 retool) was added to a suspension
of CrO 3 (600 rng 6 rnmol) in CH2CI 2 (20 rnL) end the mixture was stirred at 20* under Ar for 15
rain To this red solut=on of 4 1 phenylethanol 5 (263 mg 2 2 retool} in CH2CI 2 (2 mL) was
added In one podion and the modure was stirred for 30 rain at 20' (GC monitoring on
Carbowax 20M) Evaporation. extract,on with Et20 and evaporahon left a residue which was
dissolved In pentane and filtered through slhca Evaporation gave 260 mg of 8 (98%)
C O R E Y Enatloselectlve borane reduction
Enanboselectlve reduct=on of ketones by borane or catecholborane catalyzed by
oxazaborolldlne 3
H Ph
Ph
+ B-M 
H HO  '
1 2 3 (94%)
0
BH ph  v "Cl
4 5 (82°°)
Corey EJ J Am Chem Sc 1987 109 5551
Corey EJ J Org Chem 1988 53 2861
Corey E J Tetrahedron Left 1989 30 6275
Corey EJ TetrahedronLett 1990 31 611
Todd K Jones J Org Chem 1991 56 763
Oxazaborolldlne (3) 2 .A solution of (S) ( )2 dlphenylhydroxymethylpyrrolld=ne 1 (96 mg
0 38 retool) and methyl boronlc acid 2 (23 mg 0 38 retool) =n Phil (6 mL) was stirred at 20"C for
1 5 h m the presence of 4A molecular sieves (0 8 g) Fltralon and concentration of the filtrate
led to 95 mg of 3 (94 5%)
R(+)3"Chloro-l-phenyl-l.propanol (5) 3  Chloroprop=ophenone 4 (0 162 g 1 mmol) in
THF was added to 0 6 equlv of BH 3 and 0 1 equ=v of 3 at 0°C n THF over 20 mln After 30 mn,
one adds MeCH and 1 2 equlv of HCI in E'20 followed by removal of the volahles Addition of
PhMe afforded the cwstal line (S) dlphenylprollne (recycled as catalyst) The solul=on after
cOnCentration afforded 0 162 g of 5 (99%) 94% ee Recwstsllyzallon (hexane) gave a first crop
(82%} mp 57 580C [o])5. +24 o (c=1 CHCI3)

78 Name and Unnamed Reactwn Name and Unnamed Reacnons 79
C O R E Y Homologallve epoxldallon
Reaction of kelones with S-ylldes denved Irom Me3S + I or Me3SO + I to give epoxldes
Mel
--------*- CHO
1 3
4 5 (96%) 5
1 Corey, E J J Am Chem Soc 196 2 84 866
2 Kuhn. R Angew Chem 1957 68 570
3 Kuhn. R Leblgs Ann 1 9 5 8 611 117
40lah. G A Synthesis 19 9 0 887
2-Methyllneadamantanl epoxlde (5) 4 A mixture of 2 adamantanone 4 (1 5 g, 10
mmol), 1 (2 20 g. 10 retool) and t BuOK (97% 1 15 g 10 mmol) in [:)ME (50 mL) is refluxed with
good stlrnng under N2 for 8 h The mixture was quenched with H20 and extracted with Et2 O
(3 50 mL) Evaporation gave I 57 g of 5 (96%) mp 176°C
2-Methylldeneadamantane (6) To etheral Me2CuLI under N 2 and efficient shrrlng was
added 5 (0 4 g. 2 44 rnmol) In El2 O (5 mL) at 0°C After 30 mn Ireshly distilled SOCI2 (2 40 g.
20 mmol) was added over 5 rain Stlmng was continued for another 5 nn followed by
quenching with water extraction with EI20 and chromatography (slhca gel/pentane) to give
0 32 g of 6 (81%), mp 83oc
C O R E Y - K I M Oxidizing Reagent
Oxidation of alcohols to ketones by means of N chlorosucclnlmide (NCS) or NBS and Me2S
0 ° to 250
+ NCS + Me:,S
1 2
o
1 Corey EJ K,m, CU J Am Chem Soc 1972 94 7586
2 Jamaukl M Chem Left 1989 973
4-tert-Butylcyclohexanone (4) 1 To a stirred solution ol N chlorosucclnlmlde (400 mg
3 0 retool) in phMe (10 mL) was added at 0°C under Ar methyl sulfide 2 (0 3 mL 4 1 minor) A
white precipitate appeared immediately after addition of the sullide The mixture was cooled to
25=C and a solution of 4 ted butylcyclohexanol 3 (312 rng 2 0 mol) n PhMe (2 mL) was added
dropw=se Et20 (20 mL) was added the organic layPl" was washed with 1% HCI (5 mL) and twice
with water (15 mL) Removal of the solvent lelt 310 mg of 4 (100%) mp 44 47°C

80 Name and Unnamed Reactions Name and Unnamed Reactions 81
C O FIE Y - W I N T E R Alkene synthesis
Alkene synthesis from glycols via cyclic 1,2-thlonocarbonates
.o- I s.c.O-i
OH  O.OH "  = OH
1 Corey, EJ,W1nter JAm Chem Soc 1963 85 2677
2 Horton, O Tetrahedron Lett. 1964 2531
3 Corey, E.J. J. Am. Chem. Soc 1965 87 934
4 Hodon, D J. Org. Chem. 1970 35 3558
5 Dante, E. Tetrahedron Lett 1 972 4435
5,6-Dldeoxy.l,2.0.1sopropylldene.a.D-xylohaxofuranos.5.ene (4).2 1,2-0-
Isopropylidene-a-D.-glucofuranose 1 (11 0 g, 55 retool) and bls(imidazol-1 -yl)thione 2 (11 75 g,
66 mmol) in BuOH (100 mL), after 4 h of reflux gave 10 45 g of 3 (85%), mp 205,206°C (MeOH)
[l} - -17 3 o.
3 (5 0 g, 19 mmol) in tdmelhyl phosphlte (20 mL) under N 2 was maintained for 60 h a1150°C and
after cooling was poured into 1N NaOH (250 mL) under effiCient stirring. Extraction with CHCI3
and solvent evaporation gave 2 7B g of a crude product (TLC silica gel CH2CI2,Et20 3 1), Rf 05
Crude 4 in Et20 was treated wdh petroleum ether to gve after 12 h at 0°C 1 92 g of 4 (58%)
C O R N F O R T H Rearrangement
Thermal rearrangement of 4-carbonyl subslduted oxazoles via nitrilium yllds (2).
O
Ph OEt PhMe
1
I -OEt
2 O
.COzEt
3190%1
I Comforth, J W. The Chemistry of Pemcdlin 1 9 49 698 705
2 Dewar, M.JS J Org. Chern. 1975 40 1521
Ethyl 2-phenyl-5-(1-azlrldlnyl)oxazole-4-carboxylate (3). 2 A solution of 2-phenyl-5-
sthoxyoxazole-4-carboxylio acid chionde (1 257 g, 5 retool) in Phil (20 mL) was stirred wth
aztndine (0 215 g, 5 rumor) and tnethylamlne (0 5 g, 5 mmol) in Phil (40 rrlL) for 3 h at 20-°C.
Alter washing wth water, the solvent was removed and the residue cstaltized from petroleum
•her to give 1,032 g of 1 (80%)
A solution of I (I .032 g, 4 retool) in PhMe was heated to reflux for 17 h. After removing the
sOlvent the residue was recrystallized from petroleum ether and gave 0 928 g of 3 (90%).

82 Name and Unnamed Reactions Name and Unnamed Reactions 83
C R I E G E Glycol oxidation
Oxidation of 1,2-glyools to two carbonyl moieties by lead tetraacetate (LTA).
OH OH
1 2 3 (0",.)
+
C-- (CH--CHO
OH LTA 4
 OH cHo
OH
1 Criege, R. LiebgsAnn 1930 481 263
2 Criege, R. Chem. Ber. 1931 64 260
3 Chi-yiHsing J. Am. Chem. Soc 1939 61 3589
4 Cnege, R. Angew. Chem. 1958 70 173
5 Michallovici, M. k Synthess 1970 209
6 Naka41,N Chem Ber. 1956 89 2274
Pelergonlc aldehyde and ezelelc aldehyde (2) and (3). 3 A suspension of 9,10-
dihydroxyoctadecanoio acid I (0 674 g, 2.1 mmol) in AcOH (10 rrlL) was treated with lead
tetraacetate 2 (0.95 g, 2.9 mmol) and shaken for24 h at d. The mixture was filtered and the
filtrate was heated for 5 min at 45=C. Water (15 eL) and semicafoazine hydrochlodde (0.5 g)
was added followed by NaOAc (0 6 g) and a few drops of MeOH. After 24 h at 0=C the
semicalt)azonea ware filtered end separated by dissolving 3 in NeOH end reprecipitatlon with
HCI. Th=s gave 0.348 g of 4 (82%), mp 99-100 5"C and 0 434 g of 3 (90%), mp 163-164°C
C U R T I U S Rearrangement
Degradation of acid hydramdes or acyl azKJes to ane or amine derivatives.
HO" v -- HO
1 2
(PhO) z P.N3, TF_
F t-BuOH, 2h reflux F (63%)
I Curtlus, T Chem Ber 1890 23 3023
2 Caldweg, W.T J. Am. Chem Soc. 1939 61 3584
3 Newcastle, G W Synthess 1 g65 220
4 Thor nton, T.J Synthesis 1 9 90 295
5 Saunders, JM Chem Rev 1948 43 205
6 Cohen, L D Angew Chem 1 9 61 73 25g
7 Smith, PAS. Org React 1946 3 337
Oesoxycholamlne (2).2 To a solution of desoxycholic ac=d hydrazlde 1 (22 0 g, 54 mmol)
in I N HCt (65 mL) was added a solut=on of NaNO2 (4 2 g, 61 mrnol) In water (50 eL) under
good sbrnng and ice cooling After an addlt=Onal 15 if, n, the azlde was rmered and the wet
cake was heated gently in AcOH (210 eL) until gas evolut=on ceased. After 1 h the mixture
was filtered through a Slnter and made alkaline to pH=9 The precipitate was dissolved in
alcoholic KOH and repreclp=tated with a large amount of water Filtration, drying and
recP/staflzatlon from anhydrous MeOH afforded 39 of 2 (15%).

84 Name and Unnamed Reacnons Name and Unnamed Reactio 85
DAKIN Oxidation
Ox=dat=on of aldo (keto) phenols to polyphenols (see Bayer-Villiger oxidation).
Me Me Me-C..-O
'C = o Me4N*O'H --O'-%C'O'OH O OH
M • Me • •
1 2 3 • 4 (25"/,)
1 Dakin, H.D. Am. Chem J 1909 42 477
2 Baker, J. J. Chern Soc. 1953 1615
3 Lee, J.B. Quart. Rev. 1969 21 454
DAKIN - WEST Acylatmn
An acylative decarboxylation of u-amino acids or cў--thio acids.
S - CH2CO2H I S - CH=COMe
1 Lutidtne 2 (21%)
1 Dan, H., We, R. J. B Chem. 1928 78 91
2 er, E. J. . Cm. 1968  
3 , L. Angew. Chem. InL Ed. 19 Ј 5 4 7
4 Bn,G L. Chem..Rev. 1988 17 91
Thiophenoxyacetone (2).2 Thlophenoxyace(ic acid I (3.0 9,17.9 mmof) in Ao20 (30 mL) and
2,6-1utidine was refluxed for 12 h. After removal of the solvents the pmducl was disted to give
0.6 g of 2 (21%), phenylhydrezone, mp 82 5°C.
O A N H E I $ E R Annulatlon
Regooontrolled synthesis of five membered nngs from sllylallsnes and Michael acceptors in the
presence of "ricI4
H Me "78°
1 2 o
3 fro'/.)
HC=C==C," + "nc._. si M%
I Danhelser, R.L. J. Am. Chem. Soc; 1981 103 1604
2 Danhelser, R.L. Tetrahedmn 1983 39 935
3 Danheiser, R.L Org. Synth. 19 8 8 66 8
l"Mathyl-2-trlmethyl$11yl-ecetylcyclopentene (3). 1 Titanium letrachiorzde (0 283 g,
I. retool) was added to a mixture of 1-methyl-1otdmethylslne I (0.126 g, 1 mmol) and
methyl vinyl ketone 2 (0.07 g, 1 retool) in CH2CI 2 at -783. The red mixtme was stiffed for 1 h at
-7'C, and then was quenched by addition of water and Et2 O. Extraclion w#h Et20,
evaporation of the solvent and chromatography afforded 0.125 - 0.144 g of 3 (68-75%).

86 Name and Unnamed Reactions Name and Unnamed Reacnons 8"/
O A N I S H E F S K Y Olenes
Sllyloxydlenes in reg=o and stereo controlled Olels-Alder and hetero Olels-Alder reactions
0 MS O,V 4
0
EIIN , HO
OMe OMe
1 2 3 (68*/.) 5 (72%)
OMe OMe
MjS + H"C Ph  MeSt Ph
1 Danlshefsky, S J Am Chem. Soc. 1 974 96 7807
2 Dantshefsky, S. J. Am Chem. Soc. 1982 104 6457
Tran$-l-methoxy-3-trlmethyl$11yloxy-l,3-butadlene (3) 1 Anhydrous powdered
ZnCI2 (2.0 g, 1.5 retool) was added to TEA (115 g, 1.1 retool) and the mixture was stirred for 1 h
until the salt was suspended In TEA To this suspension was added a solution of trans-1-
methoxybutene-3-one 1 (50.0 g, 0.5 tool) in Phil (150 mL) followed by trimethyichiorosllane 2
(108.5 g, 1 mol). After 30 min the temporaJre was raised to 40"C and stirring was continued
overnight. The cooled mixture was added to Et20 (100 mL) and filtered; the combined filtrate
and washings were concentrated In vacuum and the residue distilled 1o give 58.2 g of 3 (68%),
bp 54-55"C/3 ram.
4-Methyl-4-formylcyclohex-2-ene-l-one (5). A mixture o13 and methacroleln 4 in PI1H
was refluxed for 24 h. After workup 5 was obtained in 72% yield.
O A R A P S K I Amino Acd Synthess (see Curtius)
Amino acid synthesis from ethyl cyanoacetates
0
1 2 1100%1 3 140%)
1 Darapski J. Prakt Chem. 191 5 92 297
2 Gagnono P.E. Can J Chem 19 $1 29 70
DARZENS - NENITZESCU Acylaton
Zn-Cu catalyzed FnedeI-Crafts type acylation of olef'ms wth ecyl chlorides
1 2 3 1S3%) 4
1 Darzens, G. C R 1910 150 707
2 Nenltzescu, C.D LlebgsAnn. 1931 491 189
3 Shono, T. J. Org. Chem 1983 48 25O3

88 Name and Unnamed Reactions Name and Unnamed Reacnons 89
O A R Z E N S Epoxide Synthesis
Synthesis of glycidў esters (amades) from an aldehyde or ketone and an o-haioester (art, de).
O
 Ph- HC-- C - -NF:
1 2 3 (88%)
I DalT.ens, G. C.R. 1904 139 1214
2 Tung, T.T. J. Org. Chem. 1963 28 1514
3 Gladiale, S. Synth. Commun. 1962 12 355
4 Balaster, M. Chem. Rev. 1956 55 283
5 Newman, M.S. Org. React. 1949 5 414
C15 and Tran$ Epoxypropanamlde (3). 2 t-BuOK (K16 g and ! BuOH 400 mL) was
added to I (42.4 g, 0.4 mol) and 2 (59.6 g, 0 4 tool) under N 2 at 10"C over 90 rmn. After I h
the solvent was removed at 50"C (40 in=n). Work up gave a viscous oll (67.1 g 99=/.) which
treated with Et20 (150 mL) and hexane (300 ml) gave 77 g of 3 (68.4%), mp 43-47"C.
Crystallization gave trans 3, mp 88.8-90"C and cis 3, mp 52.4-53°(3.
O A V I O S O N Oxazote Synthesis
Synthesis of tnawI oxazoles from o-hydroxyketones (benzo|ns)
Ph O. Ph
Ph- C - 0 : Ph" X'O 0  Ph Ph
1 Davldson, D. J Org. Chem 1937 2 328
2 Wiley, RH Chem Rev. 1945 37 408
O E L E P I N E Aldehyde Oxidation
Mild oxkiaton of aldehydes to catboxyhc acid using silver salts
OH OH
Ci.  .CHO Cl.. .C02H
1 2 190/,,I
1 Delepine, M. Bull. Soc. Chum Fr. 19 0 9 5 879(4)
2 Stummer, C. Unpubhshed results
3 Hamson, R.L Org. Synth. Coil. IV 493;919;972
3"Chlorosallcyllc acid (2). 2 To AgNO3 (8.5 g, 50 mmol) in water (50 mL) was added NaOH
(2.2 g, 55 mmol) in water (5 mL). Sliver oxide was filtered, washed (water), suspended in 10%
NaOH (100 mL) and heated to 60-65°C. 2-Hydmxy-3-chlombenzaldehyde 1 (7 83 g, 50 mmol)
was added slowly. After 30-40 min the maxture was h'ltered and the filtrate acidilied to pH 4.
C.'ysta,lzatlOn from water gave 7.75 g of 2 (90%), mp 178°C

90 Name and Unnamed Reactions Name and Unnamed Reactions 91
O A V I S Oxidizing reagent
2-Sulforlyloxazlndlnes as aprotic neutral oxidizing reagents; oxldatlon of alT, nes, sulfdes,
selendes and asymmetric oxidation.
3 ( %)
18P/., 15) 93"/. ee) s
N
1 Davis, F.A. J. Org. Chem. 1982 47 1174
2 Davis, F.A. TetrahedronLetL 1983 24 1213
3 Daws, F.A. J. Org. Chem. 19 86 61 4083, 4240
4 Zajak, W.W. J. Org. Chem. 1988 53 5856
5 Davis, F.A. J. Org. Chem. 1990 55 3716
6 Davis, F.A. J. Am.Chem.Soc. 1990 112 6679
ўis-4-(Nitromethyl)cyciohexanacarboxylic acid (3). 4 To a solution of 2-(phenyisulfonyl)-3-
phenyioxaziridine 2 (0.523 g, 2.0 mmol) in CHCI 3 (10 mL) was added 3-azabicyclo[3.2.2]
nonane 1 (0,125 g, 1 mmol. The reaction mixture wea atirred for 15 rain, then the aciveal ws
removed by rotary evaporation and replaced by CH2CI2. This solution was ozonized at .7rC.
The CH2C12 solution was then extracted with saturated Nsl-IC03 sofu6on. The aqueous 
was neutmlizad with HCI and then extracted with CH2Cl Z The CH2CI 2 sofution was rotary
evaporated, and the residue subjected to PLC, The major fraction that was isolated was
recryatallized from EIOH to provide 0.123 g of 3 (66%), mp 83-85°C.
O E L E P I N E Amine Synthesis
Synthesis of primary amines from alto ha,des wdh hexamelhylenetetrarnines.
F O F O
1 2 3 4
Nal 1 HCI(g) (82%)
R1CH2Br + 3  PhCH2(N'=C6HI2)*I°  PhCH2NH2
2. NaOH
I Deleptne, M. Bull. SocChm Fr 1685 13 356
2 Gatat, A. J. Am Chem Soc; 1939 61 3585
3 Hemy, A. J Org, Chem. 1990 55 1796
4 Angyal, S T. Org. Synth Coll. Vol. /V 121
2.Fluorophenacylamlne Hydrochlorlde (4). 3 A mixture of 2-fluoroacetophenone 1
(25 g, 0.16 tool) and CuBr2 (65 g, 0.29 mol) in CHCI3 (160 mL) and F.JOAc (160 mL) was
ndluxed for 4 h. CuBr was filtered, the fllUate evaporated arid the oily residue taken up in
CHCl 3 (100 mL) and filtered into hexame0denetatrarnine 3 (24 g, 0.17 tool) in CHCl3 (300
mL). Nter 16 h the adduct was filtered and washed with CHCI 3. The dried adduct was
suspended in MeOH (4.50 mL), cooled and treated with 32% HCI (63 mL). After 3 days the
supernatant ,quid was decanted from the ammonium satts, the solven removed under
vacuum and the residue extracted with 3 pollions of anhydrous EtOH (25 mL, 200 mL and
200 mL). The cooled extract afforded 12.3 g of 4 (40% overall yield), mp 197-220°C.

92 Name and Unnamed Reacnons Name and Unnamed Reacnons 93
O E M A Y O Cycloaddltion
Photochemical 2+2 cycloaddltlOn.
M CO,Me
2 •
3 (so-A) 4
1 De Mayo, P. Proc. Chem. Soc. London 196 2 119
2 De Mayo, P. Can. J. Chem.
1962 41 440
3 De Mayo, P. J.Org. Chem. 196g 34 794
4 De Mayo, P. Ace. Chem. Res. 1971 4 41
5 Weedon, A.C. The Chemistry of Enols 0Niley) 19g0 591
Cycloocta.l,-dlone-2 -(or 3-)carboxylfo acid methyl ester (3) + (4). 3 A solution of
ўyciohexa-l,3-dione 1 (1.00 g, 8.9 mmol) in methyl acrylate 2 (100 g, 1.16 mmol) was IrradBted
With a , 450 W medm pressure lamp under N 2 through a pyrex liter for 5 h. The semictystalne
residue obtained after removal of the solvent, was cystallized from MeOH, the mother liquor,
separated by preparative TLC (PhH:Et20) and the main fraction combined with the c.'ystals to
1.06 g of 3 (60%), mp 104.105oc (MeOH). The second minor fraction (lrom TLC) gave 4, mpS9-
D E M J A N O V Rearrangement
Deamlnaton of pdma/an.nes Io rearranged alcohols (via dlazonium compounds) wdh dng
contraction or enlargement for alcyclў amines
CH=NH2
1 2 (78%)
1 Demlanov, N.J. J. Russ Phys Chem. Soc. 1903 35 26
1966 30 350
2 Kottany, R. J Org Chem.
3 Sm=th, P.A. Org React. 1 960 11 164
2-Methyfoycloheptaltol (2). 2 To an ice cooled solution of 85% H3PO4 (17.52 g, 0,169
tool) and water (120 mL) was added with st.'nng 1-methyl-2-(ammomethyl)cyofohexane I (25 4
g, 0 2 tool). To the white salt obtained, a soluhon of NaNO 2 (13.8 g, 0.2 mol) In water (30 mL)
was added. Nter an hour of stimng a solution of NaNO 2 (2.76 g, 0.04 tool) in water (5 mL) and
85% H3PO4 (1 mL) was added The mixture was heated for 1 h at 95°C and extracted with Et20.
The extract was washed with HCI, evaporated and o'stllled to give 20 g of 2 (7B%), bp 73-78°C
(o ram).

94 Name and Unnamed Reacnons Name and Unnamed Reactions 95
D E S S - M A R T I N Oxidizing Reagent
Oxidation of alcuhols to aldehydes or ketones by means of penodinanes.
I KBK) AўO
HO,
COH 0
1 2 3 (87%)
4 3,4,5-(CHO)-C-C + 3  3,4,5-{CH30)3-CoH2-CHO 5
1 Dess, P.B.,Martln, JC. ,JAm Chem Soc. 1978 100 300
2 Dass, P.B., Martin, J C J. Am Chem Soc. 1979 101 5294
3 Yagupolsky, L M. Synthess 1977 574
4 Dess, P.B., Martin, J C J. Org Chem 1963 48 4155
5 Robins, JC J. Org Chem 1990 55 5186
Pedodlnane (3). 4 KBrO3 (76 g, 0.45 tool) was added over 0.5 h to 2-x:x:enzoic acid I (85
g, 0.34 mof) and 0 73 M H2SO4 (730 mL) below 55"C. The rrxlure was stilted for 3.6 h
65*. Rltration (0*C), washing (H20 1000 mL, and EtOH 2x50 mL) gave 89.1 g of 2 (93%). A
stirred slur of 2 (25 9, 89 mrno) in Ac20 (84 g, 0.83 roof) and AcOH (70 mL) was heated Io
100"C for 40 rain. Vacuum dist,lation of the sovent, filtmtinn of the slurry (N2) and washing
(Et20) gave 35.1 g of 3 (93%), mp 124-126.
3,4,,5-Tdmethoxybenzaldehyde (5). 3,4,5-Trime'jt)enzyl alcohof 4 (0.44 g, 2.23 mmo) m
CH2C2 (8 mL) was added to 3 (1.06 g, 2.47 mmof) in CH2CI 2 (10 mL) and aftar 20 rain EI20
(50 mL.) was edded. The suspension was added to 1.3 M NsOH (20 mL), the Et20 layer
washed (NaOH, wafar) and evaporaled to gve 0.42 g of $ (94%), mp 71
D I E L S - A L D E R Cyclohexene synthesis
4+2 Thermal cycloaddltlon between a dlene and an actntated alkene or alkyne, sometimes
catalyzed by Lews acids.
+ 17d 
0
2 1 3 (80%)
4 5 6 (68%)
I Dlels, O,Alder, K Lieblgs Ann 1928460 98
2 Jakobs, T.L J Org Chem 1962 27 87
3 House, H.O J Org Chem. 1963 28 27
4 Johnson, CR. J Org Chem 1987 52 1493
S Boger, D.L Chem Rev 1986 86 781
80ppolzer, W. Angew Chem 1984 96 84O
7 Wenkert, E. Org Prep Proc Inf 1990 22 131
ўll'3a,4,7,7a-Tetrahydro|ndane-1,3-dlone (3). 3 A solution of 4-cyclopentene-1,3-
ўione I (75 g, 0 78 tool), butadiene 2 (58 g, 1 1 mol) and 2,5-di-t-butylhydroquinone (free radcal
ill.or) (0.3 g) in Phil (220 mL) was allowed to stand in an autoclave for 12 days at 20-25"C A
 portion of 2 (26 g, 0.48 tool) was added and the m0dure was allowed to stand for 5 days.
Iio gave 94 4 g of cnx:le 3 (80 6%), mp 157-161aC Recjstallized, mp 160-161"C.

96 Name and Unnamed Reacnons Name and Unnamed Reactions 97
D I M R O T H Rearrangement
Mgraton of an alk-yt or aqўt group from a heterocydic to an exocydў N
+  --,---i- NH hilt
1 2 1e2%) 3 17o%)
1 Dimroth, O LiebtgsAnn 1909 364 183
2 Brown, DJ J Chem Soc. 1963 1276
3 Korbonlts, D J Chem Soc, Perkn I 19 6 6 2163
2-(Ethylaml)pyrlmldlne (3). 2 A solution of 2-ane 1 (15 0 g, 0 15 mol) and
ethyl iodide (117 0 g, 0 75 mol) m EtCH (60 mL) was refluxed for 28 h Cooling separated 1-
ethyl-I, 2-dlhydro-2-km'Knldlnlum iodide 2, 32 7 g (82 4%)
2(0.25g, 1 ixlnol)lnlN NaOH (10 mL) was heated for15 nzn on a water bath. After thepHwa
ht tOS, tllesolutk)nwasack:ledasatt.'atedsok,'tonofpicdcacd ptctrateof3.
0.23 g (70%) was lned, after recnjstallLzatton from EtOH, mp 157C
D J E R A S S I R Y L A N D E R Oxidation
RuO4 in oxidative cleavage of phenols or alkenes oxidation of aromatics to qulnones oxidation of
alkyl amides to =mides or of ethers to esters
RuO,i = HOOC
HO NalC HOOC'v 2 (62%)
.j.CO,H RoO, (o=) M.OH "oc J°,M"
Ph NalC CCI --Me=
H RuO. z H
O NalC H20 9 (45%)
1 DlerassI, C,Engle, RR JAm Chem Soc 1953 75 3838
2 Pappo, R Becker, A Bu Res Councillsr 1956 A5 300
3 Rylander, PN JArn. Chem Soc 1958 80 66B2
4 Caputo, J A Tetrahedron Lett 1952 2729
5 Caspi E J Org Chem 1969 34 112 115
6 Tanaka, K Chem Pharn'LBull lS87 35 354
3"(l"Oxo-s-methyl-Sp-carboxy-trana.perhydrolndanyl.4o.) proplonlc acid (2)3
F.ztrone 1 (1 00 g, 3 94 1) in acetone (100 mL) was ack:ed to stirred RuO4 (from RuO2 (400 )
and NalO4 (3 00 g) In water (15 mL) arx:J acetone (50 mL)]  m=xture was kept yeliow  addklg
PortZOltse NalO4 (11 5 g) II1 acetone t-120 (1 1,115 n'd.) After 4 5 h a few mL of IPH were
added Dilution wilh an equal volume of acetone, filtration tlvough Cefite, evaporation saturation
n'th NaCI, extraction with EI20..ўOEI 1 1, followed by extraction of the acid with aqueous
NaHCO3 gave 650 mg of 2 (62%)

98 Name and Unnamed Reactions Name and Unnamed Reactions 99
D O E B N E R - M I L L E R Quinoline Synthesis
Quinollne synthesis from anilines.
CHs
1 2 3 (32%)
1 Doebner, O., Miller, W. Bet. 1 883 16 2464
2 Leir, C.M.
J. Org. Chem. 19 7 7 42 911
3 Corey, J.E. J.Am. Chem. Soc. 1981 103 5599
4 Bergstrom, F.W. Chem. Rev. 1944 35 153
Qulnaldlrle (4-Methylqulnollne) (3). 2 To a solution of aniline hydrochiodde 1 (42 g, 0.324
mol) in water (100 mL) was added a solution of paratdehyde 2 (25 g, 0.5 mol) in water (100 mL)
and the mixture was maintained at rl for a week. The solution was distilled to dwness and the
reslduewas heated with ZnCJ2 (21 g, 0.15mol)at250*C. The rrlodurewasrnedeakailne and
steam distilled. The organic layer was dried over KOH and distilled to give 15.3 g of 3 (32%), bp
244-245"C (760 mm).
D O E R I N G - L A F L A M M E Allene Synthesis
Allene synthesis from oleflns via gem-dlhalocyciopropanes.
1 2 (50%) 3 134%)
1 Dodng, v.W. J. Am. Chem. Soc. 1954 76 8162
2 La Flamme, P.M. Tetrahedron 1958 2 75
3 Moore, W.R. J Org. Chem. 1962 27 4182
4 Chinoporos, E. Chem. Rev. 1 963 63 235
2-Mathyl-2,3..pentadlene (3).1, 2 To a solution of 2-methyl-2-butene 1 (14.0 g, 0.2 mol) in
a solution of KOtBu (22.4 g, 0.2 mol) in t-BuOH was added under atirdng and cooling CHBr3
(50 6 g, 0.2 mol). The mixlure was poured into water, extracted with pentane and distilled to
give 24.4 gof 2 (5[P/o), bp 63-66ў (15 ram).
A solution of 2 (24.4 g, 0.111101) In THF (50 ml.) was added to Mg tumnngS (4.85 g, 0.2 at g) in
11-1F. I'lydrolysls with water and fractK)nation afforded 2.75 g of 3 (34%), bp 72.5"C, n =
1.435.

100 Name and Unnamed Reactions Name and Unnamed Reacnons 101
D O N D O N I Homologatmn
Homologatlon of aldehydes, ketones, acyl chlondes, two carbon homoiogatlon via 2-
(tnmethylsdyl)t hlazole
S Br TMSC SM% 
OH OH
1 2 (95"/,)
O H HO,./N BnO, CHO
O 
MeO Bu4 N* F" Bu4NF,
?./_ o
"3 " 4 (84% Mel -MeCN 5 (74%) "
1 Dondoni, A J. Chem Soc. Chem Commun. 1984 258
2 Dondont, A. J Org. Chem. 1 988 53 1748
3 Dondoni, A. Terahedron 1987 43 3533
4 Dondoni, A. J. Org. Chem. 1989 54 693
5 DondonI, A. Pure&AppI. Chem. 1990 62 643
•
Dlbenzyl ўў-D-glucodlaldofuranoee (5). 3 To 3 (505 mg, 2.5 mmol) in THF (50 mL) was
added dropwise at 20"C 2 (590 mg, 3 7 retool) in THF (10 mL). After 24 h stirring, the solvent
was evaporated and the residue in "R-IF (30 mL) was treated with n-Bu4N+P (783 rag, 3 retool) in
11-1F. After 2 h stirring and work up, the residue was chromatographed (petroleum ether'EtOA
t :1) to give 602 mg of 4 (84%) (dlastereomedc ratio 95:5). To 4 (1.32 g, 4.8 mmol) in THF (50
mL) was added Nail (50%) (250 mg, 5.1 retool) at 20"C. After 20 rain reflux wore added n-
Bu4NF" (170 mg, 0.46 retool) and benzyl bromide (880 rag, 51 mmol). After 24 h at 20=C,
up and chromatography (petroleum sther:EtOAc) (7.3), the product was treated with Mel in
MeCN and refluxed until disappearance of the adduct. Work up afforded 1.101 g of 5 (74%).
complexes
/OMe
(CO)s Cr= C
1 %Ph
OMe
M (CO)
e " r 4
4
D 0 T Z Hydroqu,none synthesis
Hydroqulnone synthesis (reg,ospeclc) from a-ynes and carbonyl carbene chromium
OH
+ Ph-CC-Ph  = |Ph+ CO
Ph
2
ic,(co), 3 (62%)
MeO OH
== 
• eu MeO
S 6 (e1%)
1 D, K H. Angew Chem Int Ed 1 975 1,4 644
2 D6tz, K.H. Angew Chem. Int Ed. 1 984 23 587
3 D6tz, K.H ChemBer. 1988 121 665
4 Hofmann, P. Angew Chem Int Ed 1989 28 908
3 [X3tz, K.H. NewJ Chem 1990 14 433
Tricarbonyl(2,3-diphenyl-4-methoxy-l-naphthol)chromlum(0) (3) I Pentacarbonyl-
Imethoxy(phenyl)cabene]chrommm(O) (0.58 g, 1.86 retool) and tolan 2 (0.33 g, 1.86 mmol) in
Bu20 (6 mL) is stirred at 45°C for 3 h At -20"C, pentane (5 mL) was added. The red product
was ered and chtomatographed (silica gel, CH2CI2:pentane (1.1), to give after
Istallization from CH2CI 2 pentane (1:5) 0.55 g of 3 (62%).
Tdcarbonyl[dlmethyl.2.(l.hydroxy.4,5,g,lO.tetramethoxy.2.anthracenylmethyl).
ўўlnate]chromlum (6).3 A solution of 4 (2.12 g, 5 mmol) and 5 (1.01 g, 5.5 mmol) int-
BuOMe (25 mL) is stirred under Ar at 55C for 1 h. After cooling (-40C) the supematanl is
d'canled. The residue dissolved in CH2CI 2 was precipitated with pentane to gwe 2 26 g of 6

102 Name and Unnamed Reactions Name and Unnamed Reactions 103
D U F F Aldehyde Synthesis
Forrnylatlon of phenols and anilines with hexanethylene tetmmine.
clio OH
1 3 (lo) 4
1 DutI, J.C. J. Chain. Sot. 1832 1987
2 Dutf, J.C. J. Chem. Soc 1834 1305
3 Ferguson, L N. Chem Ray. 18 4 6 38 23O
3- and 5-Formylsallcyllc acid (3) and (4). 2 1 (10 g. 72 mmol) and hexamethylene-tetramme
2 (10 g, 71 retool) in anhyd AcOH was heated for 6 h and treated with water (80 mL) and
corm. HCI (50 mL)., F3ltration gave a mixture of 1 2 g of 3 (10%) and 2 g of 4 (17%).
DUTT - WORMALL Azldaformation
Synthesis of aromatic azldes from anilines via diazonium salts.
Ph.NH2 HNOz TINH2
1 2 3
1 Dutt, P.K,WormalI, A. J. Chem. Soc. 1821 119 2088
2 Dutt, P K. J Chem. Soc. 19 2 4 125 1463
3 Bretschnelder, H. Monatsh. 19 50 81 97O
Phenylazlda (3). 1 1 (4 6 g, 50 mmol) =n water (25 mL) and 35% HCI (15 mL) was diazo,zed
with a solution of NaNO2 (3 5 g, 55 mmol). After diazotization (stamh-iodine paper), p-
toluenesulfonamide 2 (8 5 g, 50 retool) in water (175 mL) and NaOH (6.0 g, 150 mrnol) were
added. After 10-15 rain the product was filtered Io afford 8.O g of 3 (85%), mp 85°C.
E H R L I C H - S A C H S Aldehyde Synthesis
Formation of o-nltmbenzaldehydes from o-nitrototuenea.
+ ON N Me t
OIN 1 CH=
4 (22%1 3 (STY)
1 Ehdich. P.,Sachs, F Chem. Ber 1899 32 2341
2 Sachs. F. Chem Bet. 1 900 33 959
3 Ruggli, P. Helv. Chlm. Acta. 1 8 3 7 20 271
4 Adams, R. Org Synth. Coil II 214
4,6-Oinitro-l,3-isophthalaldehyde (4). 3 A mixture of 4,6-dinitro-1,3-xylene 1 (100 g, 0 51
nx, p-ndrosodimethylanlline 2 (150 g, 0 98 tool) and Na2CO3 (100 g, 0.94 mol) in EtOH
(5OO mL) was refluxed for 8 h The product was refluxed in water (1500 mL) and stirred with
acetone (3.250 mL) to afford 130-135 g of 3 (57%). To a mixture of Phil (620 mL) and HNC3,
d = 1.12 (620 mL) was added 3 (100 g, 0 43 tool) and all was shaken for 24 h. The nitrate of
P'dimethylamlnoanlline was filtered and the crystals washed with Phil, the solvent removed in
vacuum and the residue after crystallization from Phil gave 25-29 g of 4 (22-24%), mp 129.5-
130"C.

104 Name and Unnamed Reactions Name and Unnamed Reactions 105
E I N H O R N - B R U N N E R Tnazole Synthesis
Condensation of hydrazines with dlacyclemlnes (imldss) to triazoles
CH s - NH- NH= C_H s - CO- NH- CO- CH = CI'Is' N''C'CH
(78%)
1 2 3
E L B S Condensation
Intramoleculer condensation of methyl blarylketones to polynuclssr aromatics
1 Einhom, M Lleblg's Ann 1 90 5 343 299
2 Brunner, K. Chem. Ber. 1914 47 2671
3 Brunner, K. Monatsh 1 91 $ 36 509
4 Potts, K.T. J. Chem. Soc. 1961 61 103
3.Methyl-l,5-dlphenyl-l,2,4-trlazole (3), 4 A mixture of phenyl hydmzine hydrochlonde ! Elbs, K Chem. Bet.
1 (14 5 g, 0.11 mol), N-acetylbenzamide 2 (16.5 g, 0.1 mol) and NaOAc (10 g, 0.12 mol) in AcOH 2 8achmann, W.E. J. Am. Chem. Soc
(30 mL) was refluxed for 10 h. The product was made elkaline wlh 10"4 NaOH solution and 3 Fleser, LF. Org. React.
extracted with Et20 Evaporalion gave a pale yellow oil whch slowly solidified, mp 80-81°C.
Recrystallization from 9O% EtOH and petroleum ether afforded 18 4 g of 3 (78%).
1884 17 2847
1937 59 2369
1942 1 129
1,2,3,4,5,6-Trtbenzantracene (2). 2 9-(2-Methyl-l-naphthoyl)phenantrene 1 (15.4 g, 62 mmol) and
Zn (S g) were heated for 3 h at 410"C. Distillation of lhe product et 3 mm pressure and
m::slallizetion from xylene afforded 6.4 g of 2 (44%), mp 225-228°C.

106 Name and Unnamed Reactwns Name and Unnamed Reactions 107
E L B S Oxidation
Oxidation of monophenols to polyphenols or oxidation of aromahc methyl groups by persulfates
(Caro's ac
OH F=SO, 00 o OH
1 2 (4/.)
0
Me tt
1 Ell)s, K. J. PrakL Chem. 1 8 9 3 48 179
2 Bergmann, E.J. J. Am. Chem. Soc. 1 95 8 80 3717
3 Sethna, S.M. ChemRev. 1951 49 91
4 Dermer, R. Chem. Rev. 1 95 7 57 1 O3
5 Wallace, T.W. Synthesis 1983 1000
6 Miniscl,F. Acc. ChemRes. 1983 16 27
2,,5-Dlhydroxypyrldlne (2). 2 To 2-hydroxypyndlne 1 (38.0 g, 0.4 tact) and NaOH (80.0 g, 2
rnol) in water (1500 mL) at 0C was added FeSO4 (2.0 g) in wster (20 mL) and potassium
poroxydisulfate (135 g, 0.5 tool). After 20 h at 20eC alxI filtration, conc. H2SO 4 was added (co(
to pH 0.75 and the mixture was healed to 100°C under N 2 for 30 min. The cooled solution was
neutralized by 10 N NaOH to pH 6.5 and evaporated to dryness. Extraction (Soxhlet) with iPiOq
and evaporation afforded 19 g of 2 (42%). Recrystallization from IPrOH gave 8.0 g of 2, mp 250"
260"C.
E M M E R T Reductlve condensation
Condensation of pyndlne with ketones in the presence of alumlnlum amalgam.
3(a) 3(b)
o
ч 
1 Emmert, B. ChemBer. 193972b 1188
2 Lochte, HL. J. Am Chem. Soc. 1953 75 4477
3 Russel, C.A. J. Chem. Soc. 1970 1406
4 TiIford, C.H. J. Arn. Chem. Soc. 1948 70 4001
1-(2-Pyrldyl) and 1-(4-Pyrldyl)cyclohexanol (3a) and (3b) 2 A mixture of HgCl2 (1.0
g, 3 7 retool) and AI turnings (15.0 g, 0.55 at) was heated for 15 min at 120°C. Pyddine 1
(19.0 g, 0.24 mol) and cyciohexanone 2 (17.7 g, 0 18 roof) ware added with vigorous stirring.
When the reaction began, 1 (75.8 g, 0.96 tool) was added at once and 2 (60.8 g, 0.82 mol)
was added at a rate that kept the mixture refluxing. After the addition of all of 2 (1.5 h) the
reaction mixture was allowed to cool for 2 h and was poured into a 6N NaOH solution (100 mL)
 vigorous stirring. The aqueous layer was exlracted with Phil and the Phil solution was
exlled with 6N HCI. The HCI solution was basified with NaOH pellets and after distillation
afforded a crude mixture of 3a and 3b (50.0 g). Reorystallizalion gave 45.7 g of 3 a+b
(2P/), mp 42-43=C.

108 Name and Unnamed Reactions Name and Unnamed Reactions 109
E N D E R S Chiral reagent
Asymmetric electrophlliC substitution of aldehydes and ketones via (S) or (R)-l-ammo-2-
mathoxymethylpyn'olldlne (SAMP or RAMP) hydrazones.
1 Enders, D. Angew. Chem. Int. Ed. 1976 15 549
2 Enders, D. Angew Chem. In1. Ed. 1979 18 397
Tetrahedron 1984 40 1345
3 Enders, D.
4 Enders, D. Org. Synth. 1987 65 173,1B3
5 Enders, D. Asymmetric Synthesis 1984 3 275
(S)-(+)-4.1sopropyl-3-heptanone (3). 3 SAMP-Hydrazone of 1. SAMP (2B rag, 1
mmol) and 3-pentanone 1 (86 rag, 1 mmol) were stirred at 60"C tor 20 h. (TLC or IR). The
mixture was poured Into CH2CI2ater (6:1) and the dded o,-gantc layer on evaporation and
short path distillation afforded 170 mg (87%), ўz 0 - +223* (neat).
BuU (8.4 eqtjIv) was added to dltsopmpylane (848 rag, 8.4 mol) in 1=t20 under Ar at 0*C.
After 15 min SAMP-hydrazone (1.59 g, 8 mmol) was added and stirdng continued at 0*C tor 4
then the mixture was cooled to .100"C and Prt (0.86 mL, 8.8 retool) in Et20 was added. Nter3
h at -100" and 12 h at 20"C work up gave 1.91 g of crude 2 (100%). Short path distillation
afforded 1.79 g of 2 (91%), bp 63"C/0.1 Ton', (XD - 224* (neat).
2 (1.42 g, 5.16 mmot) in Mel (3.66 g,25.8 mmo was ratluxed for 48 h and the Prl distilled. The
residue was stirred in 4 N HCI (25 mL) for5 rain and extracted with pentane. Distillation gave
0.48 g of 3 (69%), 99.5% ee.
ERLENMEYER - PLOCHL - BERGMANN AmlnoAcldSynthesls
Amino acid syntheszs from aldehydes and hydanto=n (Bergmann), synthesis of sedne
derivatives (Erlenmeyer) or of 7-hydroxyamtnoactds (Plochl)
O
NH 2 HO N-CH-Ar HO NH 2
63% 79%
NH
o N °o..p
"0  p h h
1 Plochl, J. Chem. Bet. 1 8 8 4 17 1616
2 Edenmeyer, E. Chem. Bet. 1 8 9 2 25 3445
3 Bergmann, M. Lieblgs Ann. 1 9 2 6 449 277
4 Galantay, E. J. Org. Chem. 1963 28 98
S Carter, HE. Org. React. 1946 3 198
6 BolhOfer, W.A. J Arn. Chem. Soc. 1953 75 4469
7 Langemann, A. Helv. Chlm.Acta. 1969 52 1095
B Wieland, Th. Angew. Chem. 1 9 51 63 13

110 Name and Unnamed Reacttons Name and Unnamed Reactions 111
E S C H E N M O S E R Fragmentation
Cleavage of epoxy ketones to an acetylene and a carbonyl compound via sulfonylhydrazone.
Eschenmoser, A. Helv. Chim. Acta. 1967 50 2101
Eschenmoser, A. Helv. Chim.AcL 1871 54 2896
Corey, E.J. J. Org. Chem. 1975 40 579
Cooper, M.S. Tetrahedron Lett. 1 988 22 5125
/Icetylenlў aldehyde (2). 3 To a solution of 3,5-dlnitrobanzenesulfonygydrszine (0.276 g,
1,01 retool) in THF (20 mL) was added at O°C the ketoepoxlde I (0.182 g, 1 retool). The mixture
was kept 2 h at O°C and 2 h at 20°C. The solvent was evaporated, the residue was dissolved in
CH2CI2 (15 mL) and the solution was filtered. Upon ct at -25°C the
dtrobenzenesulfonylhydrazone was filtered to give 0.404 g, mp 102C. To a solution of
hydrazone (0.404 g) in THF (10 ml.) was added NaHCO3 (0.25 g) and the mixture was stirred ў
25-30"C for 30 min. After filtration through Celite, the dear filVate was evaporated and the
residue chromatographad (sltlca gel, EtOAc:PhH,I:3) to give 2, Rf - 0.33
E S C H W E I L E R - C L A R K E Amine methylatlon
neductn/e methylation of amines by a mo:ture of fon'naldehyde and formic acid
H2  CI"I - HCOOH 
I
1 2 (60%)
Ph fOH CH:L:O Ph fOH
C HCC)CYrl C
pCI Ph j CH2CH2NH 2 pCI Ph j CH2CH2N(CH) 2
1 Escnweiler, W. Chem Ber. 1905 38 880
2 Clarke, H.T. J. Am. Chem. Soc. 1933 55 4571
3 Cope, A.C. J. Org. Chem. 1985 30 2163
4 Borch, R.F. J. Org. Chem. 1972 37 1673
5 Moore, M.L Org React. 1949 5 301
N,N-Dlmathyl-,5-amlno-l.hexene (2). 3 1-Methyl-4-pontenylamlne 1 (8 5 g, 85.5 rnmor)
was ossolved in 91% formic acid (24 g) and 37/, formaldehyde. The mixture was heated on a
•eam bath for 6 h, cooled and poured onto ice. The mixture was made strongly basic and
exlrected with Et20. After evaporation of the solvent and distillation of the residue, 6.3 g of 2
(60%), bp 135.136oc was obtained.

112 Name and Unnamed Reacnon Name and Unnamed Reactzons 113
ETARD OxJatxn
Oxdatlon (low yield) of aryl or cycloalkyl methyl groups to aldehydes with chromyl chloride
6 6 6
c,o= H=O
1 2 3
1 Etard, A.L Bull SoclChlrrtFr. 1877 27 249(1)
2 Bisagni, E Bull. oc. Chim. Fr. 1968 637
3 Nenitzescu, C.D. Rev. Roum. Chtm. 1969 14 1553
4 Ferguson, Chem. Rev. 194 6 46 237
5 Hartfort, W H. Chem. Rev. 1958 58 1
Cyclohexanecarboxaldehyde (2). 2 A solution of chromyl chloride (77.5 g, 0.5 mol) in CCI4
(155 mL) was added slowly to a solution of methylcyclohexane 1 (47 g, 0.5 mol) in CCI4 (100
mL) at 33.38"C Alter 15 mm of stirring 2-methylbuterle (0 3 mL) was added and preclpdation
of a complex began The addition of chromyl chloride required 5 h. The complex was fiitered
after 5 days, 87 g (70%). The chromyl complex was added to 400-500 g of ice and after
quenching the mixture was extracted with Et20. Alter evaporation of the solvent the residue
was diatllled in vacuo to afford 5.5-5.8 g of 2 (10%) bp 75-80"C/20 mm or 161-163"C/760 ram,
d=0.925, n - 1.45O0.
E V A N S Cl',ral auxiary
Enantoselectlve aldoi condensation by means of a chlral auxiliary and boron enolates
B Bu2
0 0 0 OH 0 0
"
 2 (88%, 99%
0 0 ,OH O O OH
.H 191%, syn, >99% eel (78%. >99% eel
I Evans, D.A. J. Am. Chem. Soc. 1 979 101 6120
2 Evans, D A. J. Am. Chent Soc. 1 9 81 103 2127, 2876
3 Newmann, M.S. J. Am. Chem. Soc. 1 951 71 4199
4 Evans, D.A. A/dnchmca Acta 1 9 8 2 I 5 23
S Evans, D.A. Tetrahedron Lett. 1 9 8 7 28 39
6 Evans, D.A. Orgamc Syn. 1 9 8 9 68 89
Syn aldol product(2).2 To a 0.2-0.5 M solution ol oxazolldone 1, mp 71-72", aD - +14.8 °,
under Ar at 0"C was added I .I equlvalent of the boron inflate, followed by 1.2 equivalent of
Isopc0pylethyl amine. After 30 mln, the boron enolate mixture was cooled (-78°C), 1 1
equivalent of benzaldehyde was added and all was stirred for 30 rrn at .78"C and 90 mm at 25"C.
 boron complex was quenched with phosphale buffer LDH 7) and treated with 30% H20 2 in
MeOH (0"C, I h). Extraction with Et20 gave diaatereomencally pure 2 (88%), mp I01°-I02C), 2
 erythro, >99% ee).

114 Name and Unnamed Reacnons Name and Unnamed Reacnons 115
FAWORSKI - WALLACH Rearrangement
Rearrangement of ў-haloketones or o.ўў'-dlhaloketones to acids or acrў adds (via
cyclopropanones).
..Oc Ko= = [C=H(s9% )
1
O
1 Favorski, A JPrakt. Chem. 1895 51 553
2 Wallech, O. I..ieblgsAnn. 1918414 296
3 Wagner, R.B. J. Am. Chem. Soc. 1950 72 972
4 Nace, H.R. J. Org. Chem. 1987 32 3438
5 Kimpo, M.D. J.Org. Chem. 1988 51 3938
6 Kande, A.S. Org. Rect. 1960 11 261
Cyclohaxanecllrboxyllc acid (2). 4 2-Chlorocycloheptanone 1 5.0 g, 34 mmol) was
refluxad in K2CO 3 (15.0 g, 0107 mol) water (20 mL) for 6 hwith stwing. Afler washing with
Et20, the solution was acidified, extracted and the solvent evaporated to give 3.O g of 2 (69%),
trip 22-24"C, bp 232-233°C.
Methyl 3.mathyl-2-btltarloata (4). : To an ice cooled solution of 1,3-dibromo-3-methyl'2"
butanone 3 (244 g, 1 mol) in B2 O (250 mL) was added in small portions (4 h) a suspension ol
NaOCH: (111.5 g, 2 mol) in Et20 (500 mL). After stlrdng for 30 more_ rain the product was
Isolated in the usual manner, 66 12 g of 4 (58%), bp 60"C/50 mm, n2 ,. 1.4382.
F E I $ T - B E N A R Y Furan Synthesis
Synthes=s of furans by condensation of an ўў-halocarbonyl compound with an enol.
HOOC .COOH
CHzBr O.C--CHz_COOC2H s 
CH2-COOH
2 1 " 3 (65%)
1 Felst, F. Ber. 1902 35 1539
2 Benary, E. Bet. 191 1 44 4B9
3 Archer, S. J Am Chem Soc 1944 66 1656
3,4-Dcarboxyfuran-2-acatlc acid (3). 2 To a cooled suspension of sodium sand (17.2 g,
075 al) in dry ether (750 mL), was added under st=rang diethyl 1.3-acetondicarboxylale 1 (155 g,
07 mol) dropwlse (1 h). When all the sodium had reacted, the mixture was cooled and ethyl
blomopyruvate 2 (145 g, 0.74 mol) was added over2 h. After 1 h reflux an equal volume of water
was added and the solvent removed Irom the orgamc layer. The residue was refluxed with 20%
HCI (200 mL) for 2 h, trealed with Nonte, filtered and cooled overnight to aflord 3,106 g (65%),
mp 200-201=(3 (monohydrate)

Name and Unnarad Reactions 117
116 Name and Unnamed Reacons
F E L K I N Cyclizatlon
Nckel catalyzed steroeselectwe synthesis ol cs and trans methyl vlnykcyclopentanes Irom
tetemerizatlon of butadiene Cycltzation (ene reaction) of unsaturated ellyl Gdgnard reagents.
3 trans
1 Felkin, H. TetrahedtonLett. 1972 1433
2 Felkin0 H TetrahedtonLeff. 1972 2285
3 Felkin, H. J. Chem. So Chem. Cornm. 1975 243
40ppolzer, W. Angew. Chem Int. Ed. 19B9 28 32
ўls or trans.2-Methylvinylcy©lopentane (33 A mixlure of (PPh3)2 NiCI2 (32.8 g, 5 mmo),
butediene I (12.42 g, 0.23 mol) and a solution of propylmagnesium bromide 1.9 M (0.25
was refluxed (room temperature, condenser cooled with solid CO2) for 24 h. After
deuten:)iysis one obtains 16.9 g of cis $ (67%). By heating the reaction mixture, which
contained the cis isomer for 24 h in a ealed tube, the thermally more stable trans isomer
obtained. The NI catalyzed ene cyczation can be performed starting with octadienyl halide=
 corlveraiort to 2. 2.4
F E R R A R I O - A K E R M A N N Thocycltzation
A general method for obta=ning phenoxthllnes, phenothmzlnes etc, by S insedlon
2 (74%)
t Fenado, E. Bull. Soc. Chim Fr 191 1 9 536
2 Akermann, F. Germ. Pat 1 91 0 234.743
J Am. Chem. Soc. 1 936 58 717
3 Sutter, C.N.
4 Deasy, C.L. Chem. Rev. 1943 32 174
$ Suter, C.M. Org Synth. Co# 1943 E 4B5
Phenoxthllne (2).3 A mixture of diphenyl ether I (1700 mL, 104 mol), sulfur (256 g, 8 rnof), and
AICt3 (512 g. 3.84 tool) was heated on • steam bath until the evolution of H2S ceased. The reaction
,ixtu was poured into ice water and the organic layer was fractionated in vacuo. The fraction bp
11S-187oc/23 mm gave 585 g of 2 (74%), after recrystaBZzation from MeOH, mp 56-57°C.

118 Name and Unnamed Reacnons Name and Unnamed Reactions 119
F E R R I E R Carbohydrate Syntheszs
Synthems of unsaturated carbohydrates by allyhc rearrangement.
OAc OAc
1 2 OEt
1 Ferner, R.J. Adv. CarbohydrateCherrz 1985 2O 67
2 Ferder, R.J. J. Chem Soc. (C) 19 68 974
3 Ferder, R.J. J. Chem Soc. (C) 1969 570
Ethyl 4,6-di-O-acetyl-2,3-dideoxy-c-D.wthro-hex-2.nopyranoside (2). 2 A solution of td-
O-acetyI-D-glucal I (5.0 g, 18 mrnol) in Phil (20 mL) and EIOH (1.8 mL, 31 mmof) was treated
with BF3.Et20 (1.0 ml). After 25 rain the optical rotation changed from -35 ° to +20.25*.
NeutraFlzation of the catalyst, filtration of the soFўIs and mmoal of the solvent left a syrup
which on tritumtion with EtOH gave 2.8 g of 2 and a second crop of 0.5 g of 2 (70%). The
pure product melted at 78-79°C and had [cў]D = +104" (Phil).
F E R R I E R Chiral cyck)hexanone synthesis
Transformation of unsaturated glycosides into cyck)hexanone derivatives by heabng in
aqueous acetone w=lh mercury (il) salts
1 Ferder, RJ. J. Chem. Soc PerlonTrans. 1 1979 1455
2 Femer, RJ. J. Chem. Soc. Perlon Trans. 1 19 8 5 2413
3 SakaidoN. J. Chem SocPerlonTranў 1 1990 1301
2,3"Dlbenzoyloxy-5-met hoxy-4-t OlUene-p.sulphonyloxycyclohexanone (2). 2
 oteflll I (10 g, 18 lI) and HgCI2 (5 g, 18 mmol) II11:2 water acetone (250 mL) were
heated to reflux for 4.5 h. On cooling 2 separated. A second crop wes obtained by dilution with
water, total: 8.1 g of 2 (83%), mp 175-176"C (from M e OH), o O - +10*C (c 2,0 Py).

120 Name and Unnamed Reacnons Name and Unnamed Reacnons 121
F I N E G A N Tetrazole Synthesis
Tetrazole synthess from azdes by dipolar cycioadditton with activaled nitnles or
intmmoieculdy wth ndriies in the presence of accLs.
F: , CsH17
N, N. N
 1 3
1 Finegan, W.G. J. Am. Chem. Soc. 1955 80 3908
2 C,apenter, W.R. J. Org. Chem. 1952 27 2085
3 Kereszly, vonK. GerrPaE 811692, C.A. 1935 29 5994
l-Octyl-5-trifluoromethyltetrazole (3). 20ctyl azide 1 (8.66 g, 56 mmol) and
trifluoroacetonitflle 2 (3.76 g, 40 mmo were heated in s sealed tube at 150=C for 17 I1.
Distillation of the-roduct yielded 2.17 g of 1 in the forerun and 8.20 g of 3 (96%), 10p 81.5-
85.,/0.25 mm, n D " 1.4272.
FINKELSTEIN . GRYSZKIEWlCZ - TROCHIMOWSKI
- M C C O M B I E Halide Displacement
Exchange of halogen m alkyl halcles (see also Makosza).
Me(CH=),(:I rB r NaCI resin Me(ClJ CPl
1 2 (10o%)
KF
3 4 (20"/.)
1 Finkelstein, N. Chem. Ber. 191 0 43 1528
2 Regen, S.L J. Org. Chent 1977 42 875
3 Gr-Trochimowski Rec Tray Ctwn. 1947 66 427
4 McComble, H. Nature 1 946 158 382
$ Sanod, M.F. Chem Rev. 1 9 51 48 237
1-Chlorodecane (2). 2 A mixture of 1-bromodecane 1 (2.3 g, 10.4 mmol) in Phil (20 mL)
and NaCl (27 g, 465 retool) in water (80 mL) was heated with polystyrene Ion exchange resin
(0.5 g)2 in a sealed tube at 110*C Ior 240 h. After cooling, separation from the resin and
distlllaon of the solvent, the residue, 1.8 g was identified as 2 (100%), bp 223°C.
1-Fluorohexene (4).4 1-ChIorohexane 3 (250 g, 2 tool) and KF (174 g, 3 mol) were heated
Under PreSSure at 250"C. Alter cool,ng the products were fraclionated through an efficient
column to obtain 40 g of 4 (20%), bp 92.5-93°C.

122 Name and Unnamed Reacnons Name and Unnamed Reacnons 123
F I S C H E R Oxazole synthesis
Oxazole synthesis from aldehydes and ўў-hydroxyamdes or cyanohydnns.
Q..-H-COII 2 + CX3H-I:n TsCW-I O'"-NH PCX31 /;--'N
1 2 3 (100%) 4 (29%)
1 Fisoher, E. Chem. Ber. 1896 29 205
2 MinovtcI, N. Chem. Ber. 1896 29 2097
3 Comforlh, J .W. J. Chem. Soc. 1949 1028
4 WIIley, R.H. ChentRev. 1945 37 410
5 Hlit, A. J.Am. Chem. Soc. 1930 52 769
2-Phenyi-5-methyloxlzoie (4). 3 A mixlure of lactamid6 1 (5.0 9, 56 mmol),
benzaidehyde 2 (8.0 g, 60 mmol) and TsOH (0.15 g) was refluxed in PhMe in a Soxhlet (w
K2CO3 in the cellouche) for 12-14 h. After cooling the filtered product gave 4 g of 3 (100%),
mp 122-125"C. Nter mcwstall',',atfon from water, mp 129-130"C.
3 (2.0 g, 11.3 retool) in POCI3 (15 mL) was heated at 80-85"C for 15 rain, the excess of POC.b
was distilled in vacuum and the residue was steam distilled. From the disttle the oxasole
was extracted with Et20 and the solvent was evaporated to give 0.5 g of 4 (28%), mp 245"C
(picrate mp 145-1460C).
F I S C H E R - B 0 R S C H E - D R E C H S E L Indole synthesis
Indole synlhesls from phenylhydrazones of ketones (Fischer), in the case of cyciohexanone
phenylhydrazones letrahydrocarbazoies are oblalned (Borsche-Drechsel).
N -N 130-135"C ,
1 H 2 (26%) CHO
reflux 2h
3 4 H 5 (69%)
1 Fscher, E. Chem Ber. 1883 16 2241
2 lyosukeSimlzu Chem. Pharm Bull. 1971 19 2561
3 SanT, COle. F. Tetrahedron Lett. 1984 25 3101
4 Robinson, B. Chem. Rev. 19 6 9 69 227
S Weich, W.M. Synthess 19 77 845
6 Drechsel, E. J. Prakt. Chem. 1888 38 69(2)
7 Borsche, W. Chem. Ber. 1904 20 378
6 Callo N.N ' Chem. Rev. 1 9 47 40 361
CIs-l,2,3,3a,4,Sb-Hexahydroo4-formyl.Sb.ethylcyclopent (b)lndole. (2). 2
Phenylhydr'ona I (850 rag, 4.2 retool) was trealed with 98% HCOOH (902 rag, 19.6 retool).
klera shorl exothemc reactfon the rrCxture was heated at 130-135°C for 35 rain. Evaporation
IW Ihe HCOOH, extraction with EtOAc and chromatography on alumina (Phil) afforded 246 n
 2 (25.6%).

124 Name and Unnamed Reactio Name and Unnamed Reacuons 125
F I S C H E R - H E P P Nltrosamlne Rearrangements
Rearrangement of N-nltroso to C-nltroso denvatlves
1 NO 2 (96"/.)
1 Fischer, O, Hepp, E. Chem. Bet 1886 19 2991
2 Willey, J J. Chem. Soc 1955 1677
3 Williams, D L H. J. Chem. Soc. D. 1969 975
4 Hughes, E D. Quart Rev. 1952 6 42
F L O O D Silyl Chlonde Synlhesls
Synthesis of sllyl chlorides from siloxanes.
H=SO= HCI
[Me2Sq20  [Me=SqzSO,  2(MeS.C + HzSO,
1 1 h 2 (67%) (NH'I)2SO4 3 (88%)
1 Flood, E.A. J. Am Chem. Soc. 1933 55 1735
2 Whltmore, L.A. J. Am Chem. Soc. 1946 68 1881
3 Sommero L.H J. Am Chem Soc. 19 4 8 70 445
Tdmethylallyl chloride (3). 1 Hexamethylslloxane 1 (162 g, 1.00 mol) was treated with
sulfuric acid (260 g, 2 6 tool) under stlrdng and cooling for one hour. The suspension of crystals
was exlraofed with pentane for 24 I1. After evaporation of the solvent, 2,181 g (67%) was
isolated. Dry HCI gas was passed through a mixture of 2 (30 g, 0.124 mol) and ammonium sulale
(20 g, 0.15 mol) in heptane 300 mL After 2 h the organic layer was distilled to give 3, 24 g
bp 57°C, d,-0.857, n) 0 ,, 1.3870.
F I T T I G Plnacotone Rearrangement
Acid catalyzed carbocaton rearrangement of 1,2-dols to ketones
Me A Me Me
2 (77%) 3 (7%) 4 (17%)
719%1 8117%1
OH HO
5 6 (60%)
1 Flffig, R. Leibg's ,Ann. 1860 114 54
2 VBanI, F.J. J. Org. Chem 1964 27 3208
3 Sand, E.D. J. Org. Chem. 1965 28 2690
4 Suzuki, S. Tetrahedron Lett. 1963 24 4997
40ah, G. Synthess 1978 358
1-Phenyl-l,l-dlmethyl|cetaldehyde (2)and Isopropyl phenyl ketone (4). 2 1-
Phenyl-2-methylwopandlol I (0.4 g, 2.4 mmol) in 97% formic add was heated to reflux for 15
rain. The mixture was poured into ice and extracted with Et20. 2:3:4 {by GC) 77%:7%:17%.
l"Cyclopenten.l.yl.l.cyclohexene (6); 2-cyclopentylcycloheptanone (7)
Ilroblcyclohexan-2-one (6). 1,1'-Cyclopantylcyclohexyldlol 5 (100 g, 0.657 tool) was
IMiuxed In 25% H2SO4 for 2 h. Et20 extraction and evaporation of the solvent gave 60 g
(60%) of a mixture of 6,7 and 8 in a ratio of 80.2%, 2.6°/, and 17.2%.

126 Name and Unnamed Reacnons Name and Unnamed Reactions 127
F O R S T E R DlaZO Synthes=s
F0rmatlon of dlaZO denvaWas from oxlmes
"OH N_ч
N
1 2 (50%)
 N-OH 
NaOCI
OH
1 Forster, MC.J. J. Chem. Soc. 1915 107 260
2 Melnwaid, J. J. Am Chem. Soc. 195g 81 4751
3 Hassner, A. Tetrahedron Lett. I g6 2 75g
4 Kirrnse, W. Angew. Chem. 1957 69 108
5 RundeI, W. Angew. Chem. lg62 74 46g
Olazofluorene (2). 2 A suspension of fluorenone oxirns 1 (0.5 g, 2.5 mmol) in 15 N NH40H
(25 mL) was treated with 5.25% NaOCI (100 mL) at 0C for a pedod of 1 h. The reaction mixture
was exlracted with petroleum ether and the solvent evaporated to leave 0.1g g of 2 (50%).
Unreacted oxime 1 was recovered from the aqueous solution (0.25 g).
F O R S T E R - D E C K E R Amine Synthesis
SelectNe monoallo/latlon of primal/amines via tmlnes An alternative method is the reaction
of 1 and 2 in the presence of NaCNBH4 or tnacetoxyborohydride (Borch reduction). 4
11o*
Ph - CH 2-CH.z-NH2 + OCH-Ph  Ph-CH2-CH 2-N = CH-Ph
2 1 3
4 (eo%)
1 Forster, MO. J Chem. Soc. 1899 75 934
2 Decker, H. LJeblgs Ann. 1913 395 362
3 Morrison, A.L J Chem. Soc. 1960 1478
4 Borch, R.F. J. Am. Chem. Soc. 1971 93 2897
N-MethyI-N-phenethylamine (4), 3 Benzaldehyde I (116 g, 1.1 mol), p-phenetylamine (121
g, 1 tool) mid PhMe (5OO mL) were refluxed with a Dean-Stack water separator untill ell water
had distilled. Under stirring, dlmethyl sulfate (126 g, 1 tool) was added dropwise and reflux
was continued for another 3 h. Water and NaOH was added until the pH stabilized st pH=7.
Alter hydrolysis, the solver/snd I was recovered by steam distillation. The residual water
Iotution was made alkaline to give 114 g of 4 (80-85%), bp 203"C, t: 1.51620 d : 0.930.

128 Name and Unnamed Reactions Name and Unnamed Reacnons 129
F R A N C H I M O N D Cyano Succinic Acid Synthesis
Condensation of c-haloesters to succln=c acid dervalives in tPte presence of CN-
2
1872 5 1049
1930 52 4074
1 Franchlmond, A.P N, Chem. Ber.
2 Fuson, R C. J. Am. Chem Soc.
Dlethyl 3.methyl.2-cyano-l,2-cyclobutanedlcarboxylate (2) 2 Diethyl a,a' dibromo-
IFmethyladtpate 1 (20.0g, 55 mmol) and powdered NaCN (8.0 g, 160 rnmol) in abs. EIOH (15
rnl.) were heated to reflux for 24 h to give after f'dtrallon of inorganic salts and evaporalion of the
solvent 8.0 g of 2 (63%), bf) 140-143"C/3 ram, n2,, 1.44735.
F R E U N D - G U S T A V S O N Cyclopropane Synthesis
Cyclopropane synthesis from 1,3-dlhaloalkenes with metals
1 Freund, A.
2 Gustavson, G.
3 Haas, H.B.
4 Bartleson, J.D.
S Wiberg, K.
Morlatsh. 1882 3 625
J. Prakt. Chem. 18 87 36 300
Ind Eng Chem. 193S 28 1178
J. Am. Chem. Soc. 1946 68 2513
Tetrah edron Lett. 19 6 3 2173
1,1,2-Tdmethylcyclopropane (2). 4 To s suspension 04 oxygen-free zinc dust (196 g, 3 st) in a
ndxture of water (100 mL) and n-PrOH (300 mL) cooled in an ice bath, was added 1,2-melhyi-
2,4-d'd)romopropene 1 (224 g01 mol) over a penod of 90 rain. The mixlure was stin'ed for
about 32 h at 20°C and the hydrocarbon was isolated by distillation. The fraction bp 49-510C
as soflected, 79.1 O (66%). After washing with waler0 freezing out the water and distiflation
thh a column with 100 theoretcal plates pure 2 was obtained.

130 Name and Unnamed Reactions Name and Unnamed Reacuons 131
F R E U D E N B E R G - S C H ) N B E R G Xanthate Rearrangement
Rearrangement of S-methyl xanthates to S-methyldlthlocarbonates (conversion of alcohols Io
thols via xanthates, also phenols to thophenols via thK)carbarnates).
1 2 110%1
1 Freudenberg, K. Chem. Ber. 19 27 60 232
2 SchOnberg, A. Chem. Ber. 19 30 63 178
3 Arek, Y. Bull Chem. Soc. Jpn. 1970 43 3214
4 Taylor, R. J. Chem. Soc. PerldnTrans. 2 1988 183
5 Wiersum, U.E. J. Org. Chem. 1989 54 5811
S-(S-Chloro-l-hexyl)-S'-methyl dithiocarbonate (2). 50-(6-Chloro-l-hexyl)-S-rnethyi
xanthate I (60.0 g, 0.265 mol) was distilled at 525"C for 3.5 h into s quartz tube. The cnx:le
pyofizate (45 g) was fractionated, yielding 25.3 g of I (81%) and leaving a yellow residue
which after distillation gave 5.9 g (10%) of 2, bp 175-176°C (20 ram).
F R I E D E L - C R A F T S Alkylation-Acylatlon
Alkyaton or acylatlon of aromatic compounds by means of alo/ halKles, alcohols,aikenes, acyl
haldes in the presence of Lewis acids
OH
O'C
MoO MoO
 + || ZnC
OMo CI C Ph 110 =C
1 2 3 ()
1 Fdei, C.,Cs,J.N CR. 1577 84 1450
2 Gmggms, PT. IndEngChem. 151 43 1970
3 ReN,WB. J.AmChem.S 151 73 318
4 Ku,M JOChem 186 51 2128
 m,P. Chem.Rev 155 55 229
 Pen, D.E. Syness 1972 533
7 Pe, C.C. O.Rct. 1946 3 130
|'Mlthoxy-5-t.butylbenzophenone (3). 4 A solution of 4-methoxy-t-butylbenzene 1 (100
g, 0.604 mol), benzoyl chlodde 2 (85 g, 0.605 rnol) and ZnCI 2 (0.2 g) in 1,1,2,2-tetrachioroethane
(150 mL), was refluxed for 40 h After removal of the solvent from the reaction mixture, the rasldue
was ўstllled. The fraction bp 208-210°C (12 mm) gave 132 6 g of 3 which crystalCl:ed on standing.
Rec/stallizstlon from MeOH gave 107 g of pure 3 (66%).

132 Name and Unnamed Reactions Name and Unnamed Reacnans 133
F R I E D L A N D E R Culnollne Synthesis
Qulnollne synthesis from condensation of o amlnoaryi aidehydes (ketones) with (z methylene
aldehydes (ketones)
CHO
чO
NH= heat Me
1 2 3 (,')
1 FnedlAnder, P Chem Bet 1 8 8 2 15 2572
2 Madў.graf.JH J Org Chem
1969 34 4131
3 Coffen, D L J Org Chem 19 7 4 39 1785
4 Bergstrom, FW Chem Rev 1944 35 151
5 Eckerl. K Angew Chem Int Ed 19 81 20 208
2,3-Olmethylqulnollne (3). 2 A solutmn of o-aminohenzaldehyde 1 (1 0 g. 8 2 mmol), 2-
butanone 2 (0 59 g, 8 2 retool) and 33% aqueous KOH (5 niL) in 95% EtOH (20 mL) was
refluxed for 1 h The reaction mixture was neutralized with AcOH concentrated and extracted
with Et20 The resx:ue after chromatography ymided 0 75 g of 3 (SP/), mp 68-69'
F R I E S Phenol Esler Rearrangement
Rearrangement o! phenol esters to o or p ketophenols Lewis acid catalyzed
CH 0 CH=O
O-C-CH & CHI
1 2 1186%1 3 lOS'/.)
1 Fnes K Chem Bet 1908 41 4271
2 Cremer, SE J Org Chem 1961 26 3653
1986 27 1959
3 Madln, A R Tetrahedron Left
4 Blatt AH ChentRev 1940 27 429
S Effenberg Angew Chem Int Ed 1973 12 776
6 Blatt. AH Org React 1942 I 342
3,5-Dlchloro-2-hydroxy-6-methyl acetophenone (2) and 6,8-Dlchloro-2,5-
dlmethylchromone (3) A rmxlure of 2,4-dtchioro 5-mathylphenyl acetate 1 (39 6 g,
0181 mol) and NCI3 (32 0 g 0 24 mol) was heated for 90 rnlll at 135°C The cooled solution
was poured into =ce (150 g) and extracted with B2 O The Et20 solution was washed wdh
10% NaOH and evaporated to give 1 0 g of 3, mp 125-135°C, after recl3tstallizatlon from
EIOH. 200 mg (0 5%) of 3 and unreacted 1 3 4 g (8 5%) From the NaOH solution after
accllrlcatlon with 6N HCI and exlractlon with Et20 was obtained 8 2 g of 2 (18 6 %), mp 104-
105 $*C (racrystalllzed from petroleum ether)

134 Name and Unnamed Reacnor Name and Unnamed Reactions 135
FRITSCH - BUTTENBERG - WIECHELL AcetyleneSynthesls
Alpha elimination from haloethylenes leading via cadene rearrangement to acetylenes
p ci - CH,= Br auU
• _ •  p cI - CsH, = - C===C - CsH s
CHs/C--C'H
1 2 (22"/,)
1 Fntsch, P. LielgsAnn. 1894279 319
2 Buttenberg, W.P. Llelgs Ann. 18 9 4 279 327
Liebigs Ann. 18 9 4 279 337
3 Wechell, H.
4 Curtin, D.Y. J. Am. Chem. So 1958 80 4599
5 Kobdch, G. Chem. Ber. 1972 105 1674
6 Kobrich, G. Angew. Chem. lnt. Ed. 1965 4 49
1-Phenyl-2-(p-ўhlorophenyl)acatylene (2). 4 To a solution of Z-l-phenyl-l-p-
cNomphenyl-2-bromoathylene I (5.00 g, 17 tool) In ether (100 mL) at -35°C under N 2 was
added a 10% solution of butyBthtum (26.5 mL) maintaining the temperature at -20°C to -35"C
ior 30 mE. The mbure was a,owed to warm to room temperature and was neutralized with
20% HCI (50 mL). Separation of the neutral fraction with ether io,owed by dylng over
anhydrous sodium sulfate and removal of the ether gave 8 resaue of 2.24 g. Purification by
chromatography on eiumina yielded 0.88 g of 2 (22%), mp 82-83°C.
F U J I M O T O - B E L L E A U Cyclohexenone Synthesis
Synthesis of fused cyclohexenones from lactones (an alfernatlve to the Robinson annulalon).
1 Fullmoto, G.I. JAm Chem. Soc. 1951 73 1856
2 Belleau, B. J. Am Chem. Soc. 1951 73 5441
3 Weyt Rayrtal, J. Synthess 19 5 9 49
Cholestenone (3).1 Methylmagnesium iodide obtained from CH31 (142 mg, 1 mmol) was
added dropwise I0 a solution of enol lactone (Tume's lacone) 1 (386 mg, 1 retool) in B20 (3
mr.) under N 2 at 0*C. The nxlure was let stand lor 24 h and was decomposed wdh NH4CI
solutmn. Removal of the solvent gave crude 2, wh,ch on recrystallization from Me2CO afforded
180-260 mg of 2 (45-65%), mp 174-178°C. Crude 2 was stirred with a solution of 20% NaOH (5
mL) and MeOH (30 mL) for 24 h. The residue, obtained after removing the solvent, was
ўhromatographed on alunna (petroleum ether Phil 9 1 or 4:1) to give 3, mp 80-88°C.

136 Name and Unnamed Racnons Name and nnamed Reactions 137
F U J I W A R A Lanthanўle (Y'o) reaction
Use o! ytterbium or other lanthanozds in substitution, reduction and 1,2 addition.
,o, /'°\ .o o.
ph/CNph
Ph.--{Ph
1 2 Ph'3 4 Ph Ph
OHO
I II
1 + 2 + Ph'CHz CN  Ph-C-C-CH2"Ph
5 pI h 9 (65%)
1 Fupwara, Y. Chem. Lett. 1981 1771
2 Fuvara, Y. J. OrgChern. 1984 49 3237
3 FuJiwara, Y. J. Org. Chem. 118 8 53 6077
4 FuJiwara, Y. J. Org. Chem. ll87 52 3524
2-Oxo-l,l,3-trlphenylpropan-l-ol (6). 3 Yb powder (173 rag, 1 mmol) under N2 was
.eated with a drop 04 Mel and w=Zs heated to acthrate the Yo. THF (2 mL) wlB added, foliowed
by HMPA (1 mL). Under stirring benzophenone 1 (182 rag, 1 retool) in THF (2 mL) was added,
1041owed by phenylaceto-nlldle 5 (117 rag, 1 retool). Nter 4 hitching t 20,C the mixttlm was
quencNKI with 2N HCI, extracted with Et20 and the i:xoduct separated by medium pressure
LC.to afford 187 mgof 6 (65%) and 50 mg 044 (35%).
F U J I w A R A ArylaUon, Caoxylation
A mild Pd catalyzed arylation or carboxylation of a Pd activated double bond.
[ pd(OAc)2  PhPdOAc + HOAc
+
IO I Ph O
1 2 (504)
+ CO (3oa.) ,,
1 Moltad, I., Fulwara, Y. TetrahedronLett. 1987 1119
2 Yamamure, K. J. Org. Chem. lS78 43 724
3 Fujk,,nlrў Y. J. Organomet. Chem. 19 8 4 288 C44
4 Fujuwara, Y. Chem. Left. 1989 1667
1,1-Olphenyl-2.benzoylethane (2), 2 A mixture o! benzylldeneacetophenone 1 (2.08 g,
10 retool) and i:)lladlum acetate (2.0 g, 10 retool) in benzene (150 mL) end AcOH (40 mL) was
fluxed under Itlrdng unlg the preclation 04 Pd metal ceased. The  Pd was filtered
ў Icx:l the  ter whlng wllh waler w ўonntral in vaojum. The residue,
 on slina gel (hexane) gzzve a small amount 04 biphenyl, followed by 1.40 g Of
| (50%), eluted with hexane:benzene (1:1).

138 Name and Unnamed Reactions Name and Unnamed Reacnons 139
F U J I W A R A - H E C K Coupling
Cross-coupling reactions of aromat=c or vtnyllc hal=des and olellns catalyzed by palladium.
CI "i "CI + Ph" Pd (OAc k ==
Ph
O R3N, 140" Ph (44%)
TTP; TEA NBu=
= 1
!
+ .''CO=Et =
Br E N; DMF (98%)
1 Fuwara, Y.
2 Heck, R.F.
3 Heck, R.F.
4 Hassner, A.
5 Fu,,ara, Y.
6 de Meijere, A.
7 Heck, R.F.
Tetrahedron Lett. 19 8 7 1119
J.Am. Chem. Soc. 1988 90 5518
J.Am. Chem. Soc. 1974 98 1133
J. Org. Chem. 1984 49 254B
BulI. Chem. Soc. Japan 1990 63 43B
Syn/ett 1990 405
Org. React. 1982 27 345
Trans-4-[p(DI-n-butylamlno)atyryl]pyrldlne (3). 4 A mixture o! p-bromo-N,N-dlbutyl
aniline I (S.88 g, 20 retool), 4.vlnylpyddlne 2 (2.63 g, 25 mmol), Pd(OAc)2 (45 rag, 0.2 mmol), tfl
o-tolylphosphine (120 rag, 4 retool) and triethylamine (t 0 mL) was heated at 1100C lor 72 h. To
e cook)d mixture was added water and CHCI 3 (all solids cissolved). The water was extrKI
with CHCI3 (2x100 mL) and the combined organic solution was washed, dried and evaporat:L
The residue recrystalllzed from cold hexane gave 5.29 g of 3 (86%), mp 80.81"C.
G A B R I E L Amine Synthesis
SynlheSlS of primary amines from alkyl halldes
o
1 2 o
4
3
t Gabdel, S. Chem Ber. 1887 20 2224
2 Bradsher, C H. J. Org Chem 1 98 1 46 327
3 Gibson, J.S. Angew Chem Int Ed 1 9 6 8 7 9 t 9
4 Ragnarsson, A. Accts. Chem Res. 1991 24 285
2-(2-Bromophenyl) ethylamlne (4). 2 A mixture of 2-(2-bromophenyl) )ethyl bromide 1
(90 65 g, 0 34 tool) and potassium phthalimu:e 2 (66 64 g, 0 36 tool) in DMF (2B0 mL) was
Iln:l lot 15 h at 90"C. Dilution with CHCI3 (400 mL), washing with 2N NaOH and evaporation
gave 94.27 g of 3 (83%), rectstallized !rom MeOH/petroleum ether (3.7), mp 96.5-9B°C.
A mixture of purilled 3 (83.64 g, 0.253 tool), MeOH (250 mL) and hydrazine hydrate (30.43 g,
0.506 tool) was refluxed for 1 h. The residue obtained after evaporation of the solvenl was
It(luxed wllh conc. HCI (120 mL) !or 1.5 h. The sol=d was lillered and the filtrate was made
 w=th 2N NaOH and cooled to 5°C !or 3 h. Extraction with EI20 and evaporation of the
Iolvent gave 41.87 g of 4 (83%), bp B2-86°C (0.3 ton').

140 Name and Unnamed Reacnons Name and Unnamed Reactions 141
G A B R I E L - C O L M A N Rearrangement
Synthesis of Isoqulnolines by rearrangement of phlhahmides.
O O
  heat N'CH2--) - CeH4-NO2"p "
(3 O
1 2 3 (S6%)
OH
NaOMe  - CsH-NOz--p
 ---- NO
ON
1 GabdeI, S.,Colman, j. Chem Ber. 1900 33 980
2 HilI, J.HM. J Org,. Chem. 1965 30 620
3 Allen0CF.H. ChenzRev. 1950 47 284
3"(p'Nltrobenzoyl)-l,4-dlhydroxylsoqulnollne (4).2 p'Nitro--bromoacetophenone 2 (18.2
g, 75 mmol) and potassium phtailrnidate I (9.3 g, 50 mmol) in Me2CO (150 mL) were refluxed
for 72 h. The brown mixture was poured into water, the solid was filtered and tntumted with
Et20 to remove unreacted 2. The tan residue after recstallization from DMF gave 8.7 g of 3
(56%), mp 243-244oc.
A solution of :3 (1.95 g, 4 retool) in 2N MeONa (56 mL) was refluxed under N 2 for 2 h. The
cooled mixture was neutralized with dilute I-ICL the solid filtered and washed with water.
Recn/atalilzation from AcOH affon:led 4, rnp 278-280"C.
G A R E G G - S A M U E L $ $ O N Olefln Synlhesls
Conversion of v=c Irans-dlol groups into a double bond by K)dlneqnphenylphosphlne-lmKlazole
reagent.
oH
HO,O Ph3P'I2
 OBz Z o OBz
1 2 (56%) 3 (17%)
1 Garegg, P.J., Samuelsson, B Synthesis 1 9 7 9 469, B 13
2 ZanskJ, A. Carbohydrate Research 1 9 9 0 205 410
Benzyl 2.benzyloxycarbonylamlno-2,3,4,6-tet radeoxy-6-1odo-a-D-eryt hrohex-
3-enopyranoslde (2). 2 To a mixture of mphenylphosphine (15.72 g, 59.9 retool) and Iodine
(15.2 g, 59.9 retool) in PhMe (200 mL) stirred at 20"C for 30 min, was added a solution of
imidzole (4.5 g, 66.1 retool) in MeCN (50 mL) and stirring was continued for 10 min at 50C
Benzyl 2Joenzyioxycarbonyl-amino-2-deoxy-o:-D-glucopyranoside I (4 04 g, 10 mmol) was
added to the reagent prepared above and the mLxture was stirred for 3 h at 80"C The mLxture
was cooled to 2(PC, filtered through Cellte and concentrated in vacuum. The residue was
extracted with PhMe and the combined extract evaporated to dryness. The residue
chromatographed on silica gel (PhMe EtOAc 95:5) gave: 2.68 g o( 2 (56%), mp 129-130°C0
0 - +22" (c 0.8 CHCl3), 1.03 g ot 3 (17%), mp 119-121"C, 003..133 ° (c I CHCl3) and 33O
rng o( -2 (7%), mp 138-140°C, (z30 = - 151 ° (c 2 CHCI3).

142 Name and Unnamed Reacnons
G A $ S M A N Oxlndole Synlhesls
Synlhesls of OXlndoJes from anilines
 c-ocl 2 TF 4
NH2 CH3"S-CH=-COOC2H s 3
1
1 Gassman, p G. J. Am. Chem. Soc.
2 Gassman, p G J. Am. Chem. Soc
3 Johnson, p D. J. Org. Chem.
SCH=
N °
7 (7S'/.)
1973 95 2718
1974 96 5508
1990 55 1374
Oxindole (7). 2 To a stirred, cooled (-65"C) solution of aniline 1 (4 09 g, 44 retool) m CH 2CI 2
(150 mL) was added dropwtse t-bulyl hypochionte 2 (4 77 g, 44 retool) in CH2CI 2 (20 mL). After
10 nn, ethyl methyithoacetete 3 (5.89 g, 44 mmol) in CH2CI 2 (20 mL) was added (exothermic)
and stirring was corinued for I h. TEA 4 (4.44 g, 44 retool) in CH2CI 2 (20 mL) was added. The
mixture was a/lowed to warm Io room temperature, water (50 mL) was added and the organic
layer was evaporated. The residue was redissolved in EI20 (150 mL) and was stirred with 2N
HCI (20 mL) for 24 h Filtration afforded 6 61 g of 6 (84%). A solution of 6 (2.00 g, 11 retool) in
anh. EIOH (50 mL) was stirred and refluxed with W-2 Raney nckel (12 g) for 2 h. The
supematant and the washing solution were evaporated to dynass, Ihe residue was dissolved
in CH2CI2 (20 mL), the solution dded (MgSO4) , fillered and evaporated to give 1.13 g o 8
(76%), mp 116-117.C.
Name and Unnamed Reacnons
G A S T A L D I Pyrazlne Synthesis
Pyrazme synthesis from -oxlmlnokelones via cў-am=noketones
1 2
KC_ Et... N CN
N Et
3 (8%)
1 Gastak,G. Gazz. Ch/nt/ta/ 1921 51 233
2 Shaq), W. J. Chem. Soc. 1948 1862
3 Krams, I., Spoerd, p. Chem. Rev.
1947 40 301
2,5"Dlcyano..3,8-dlethylpyrazlne (3).2 To ethyl 3-oxopentanoate 1 (40 O, 0.312 tool)
in 2.5% NaOH (600 mL) kept for 24 h, were added NaNO2 (21 g, 0.304 tool) in water and after
cooling at 5"C a 20"A solution of H2SO 4 (172 g) dropwse. The mixture was stirred for 60 rain
at 5"C, extracted w#h B20 and after removal ol solver, Ihe residue was distBed to give 15.7
g o( 2 (44.6%). To Na2S20 fi (183 g) and water (317 mL) was added 2 (40 g, 0.396 tool). The
mixture was heated, then kep 24 h at 20oc and treated wCh EtOH (1500 mL) and AcOH (7.5
mL). After 24 h the predl:)itate was filtered. From the mother liquor a second and third crop
were obtained. The crode product (50 g) was treated wth KCN (22 g) in water (100 mL) with
Slbdng at 40-50"C and the red brown solution was heated for 1 h at 45-60"C with 20'/= HCI (27
mL) to give a solid. The falter was extracted with FJOH to give 2.82 g o 3 (8%), mp 115"C.

144 Name and Unnamed Reactions Name and Unnamed Reactions 145
GATTERMAN - KOCH Carbonylation
Synthesis of aromatic aldehydes or ketones using cyanide salts or CO - HCl and Lewis acids.
HCI  CHO
1 2 (50%)
3 4 CH 5(58%) O
1 Gaftermann, L. Chem. Ber 1 8 9 8 31 1149
2 Adams, R. J. Am. Chem. Soc. 1923 45 2373
3 Kreuzenberg, A. Angew. Chem. 1967 79 978
4 Truce, WE. Org. React. 1957 9 37
5 Gatterrnsnn, L.,Koch, J. Chem. Ber. 1897 30 1622
6 Brunson, H R. J. Org. Chem. 1967 32 3359
7 Gore, PM. Chem. Rev. 1955 55 235
8 Grounse, N. Org. React. 1 949 5 291
Resorclnaldehyde (2).2 To resorcinol 1 (20 g, 0.18 tool) In Et20 (150 mL] was added
Zn(CN)2 (37 g, 0.27 tool) and dry HCI gas was bubbled through for 2 h After decantation the
residue was (:zyslallized from water (100 mL) to afford 12.5 of 2 (5(P/o), rnp 135-137°C.
2-Methyl-2-phenyllndanone (5). 8 To vigorously stirred benzene 3 (140 g, 1.8 tool) and
AICI3 (42 g, 0 3 tool), was added 1,2,2-tdchicropropans 4 (44 5 g, 0.3 tool) over 3 h at 24-
27"C while CO was rapidly bullied in. The organic layer after quenching with water, was dded
and distilled in vacuum Crystallization from EtOH gave 39 g of 5 (58%), mp 111"C.
G E W A L D Heterocycle Synthesis
Synthesis of 2-amlnofurans (thlophenes. pyrroles) by condensation of maiononitnles with
ketones.
+ CH= + S
1 2 3 4 12%1
Me O .CN
+
'OH CN  N H 2 52
"C-----o CN C N
.CH mNH 2 CN N H =
H 63
1 Gewald, K. Chem Bet. 1965 98 3571
2 Gewald, K Chem Bet 1966 99 94,1002
3 Gewald, K. Z Chem 19 61 I 349
4 Peet, PN. J Heterocycl. Chem. 1968 23 129
2-Amlno-4,S,6,7-tetrahydrobenzo-(b)-thlophen-3-carboxyllc acid ethyl ester
(4).4 A mixture ot ethyl cyanoacetate 1 (56 6 g, 0 5 tool) cTciohexanone 2 (49 1 g, 0 5 tool),
moq0holine 3 (43 5 g, 0 5 mol) and $6 (16 g, 0 5 at) n EtOH (150 mL) was stirred and the
temperature rose to 50°C After 1 h a th=ck precipitate was present. After standing 24 h, the
mixture was poured into water and the solid filtered The crude product, 115 g, recrystallized
from EtOH gave 95 2 g of 4 (82%), mp 114-115°C

146 Name and Unnamed Reactions
GIRARD . SANDULESCU Reagent
Reagents "T" and "P" for separation of aldehydes or keto.es  formln a water soluble
hydrazide derivative.
.p
1 I'o° CHNM% Cf
G, , S, G., He . A.
1 936 19 1095
2 Lerer, E. B.Cm. Fr. 1949 1400
ller, O.H. Cm. R.
1 9 62 62 205
mI, L. J..Cm. 1991 56 1419
(Carboxymethyl)trfmethyfammonlum chloride hydde (Reagent -).I A
 lbn of el bmacate (984 g, 6. 1) was  w tdtle (2
3.39 1). er 12-24 h a s n  tdtl  g, 3.3  w a.
er te ubn of  bete, dine ( g) was . 
 was ter a d u vm (H2SO4)  aflo 11 g of  (/).
Pamlon of aldehyde.2 Nmnzede (302 )  ree  (502 )
w  in EH (5 mL) uer . er olt the w le ho 2 (
),  2-0C was obin.  mss gave ba  ehyde.
Name and Unnamed Reactions
o ac ' G L A S E R - C H O D K I E W C Z Acetylene Coupling
Ply eopenes from monoacelylenes |n the presence of copper salts.
Me2-C-- C CH Cu2CI2
,  -c=c-c=c.c,.,
1
2 (90%)
Ph-CCH
Et3Sr-'C C- Ca C - Br Ph --C:=j C- Ca C- Ca C" SI Et 3
3
4 (30°/,)
1 Glaser, C. Chem Bet 18 6 9 2 422
2 $tansbuy, H A. J Org Chem 1 9 6 2 27
3 Chodldewcz, W 320
Ann Chlm. (Pans) 1 957 2 819(13)
4 Walton, D.R M. Synthesis 1974 890
,7"Dimethyl-3,5-.octad|yne.2,7.dlol (2).2 2-Methyl-3-butyn-2.ol 1 (84 g, 1 roof), pyrldine (20
g, 0 25 rid), MeOH (78 g) and C u2CI 2 (1 2 g, 12 rnmol) was stirred at 30-35=C for 2 5 h while
7 0 L (0 28 tool) of 02 was absorbed After treatment wdh saturated NH4CI (4OO mL),
extraction with Et20, evaporation and recrystallizatlon from Phil (1200 mL), 75 g of 2 (9O%),
mp 127-129oc was obtained
l"Phenyl-6-b'lethylsllylhexab.iyne (5).4 Phenylacetylene (2 6 g, 25 rnmol) was added
dropwise to BNH2 (1 1 g), Cu2CI 2 (0 2 g) and NH20 H HCI (0 5 g) in DMF (25 mL) followed by
bromobutadiynyt tnethylsilane 3 (6 1 g, 25 retool) After 2 h the mixture was acidified at
With 2N H2SO4 (100 mL). Extraction with EI20 and chromatography on acidic alumina
(Petroleum ether) gave 1.98 g of 4

148 Name and Unnamed Reacons
Name and Unnamed Reactions 149
G O L D Reagent
Reagent for dlago/iaminomethynilation Of activated methylenes or NH 2 groups.
CI N CI CI-
"11" " . 6... 65* +
N N 1  Me2N=CH--NCH--NMe2
CI 2 3 (66%)
P'Br'CaH4-CO-CH'j + 3  p-Br-CH,-CO-CI-I==CH-N Me t
4 5 (74%)
Ph.NH2 3
 Ph-N=CH-NMe 2 Ph--NH-NH2 
Ph--N,,,N
1 Gold, H. Angew Chem. 1950 72 959
2 Eschenmoser, A. Angew. Chem. Int. Ed. 19 71 10 330
3 Kunst, G. Angew. Chem. InL Ed 1 977 15 239
4 Bryson, T.A. J. Org. Chem. 1990 45 524
5 Gupton, J.T. J. Org. Chem. 1990 45 4522
3-(Dlmethylamlno)-2-azaprop-2-an-l-ylldana dlmathylammonlum chloride (3), s
1 (148 g, 0 808 tool) in dioxane (800 mL) at 25°C, with DMF 2 (385 g, 5.2B mol) was heated for
45 min at 65°C (CO2 evolution). After 2-3 h at 88-65°C and coogng, 3 crystafllzed 339 g (86%),
mp 94.95oC.
Ketone (5). 5 To MeONa (from 1.5 g Na and 100 mL MeOH) was added p
Ixomoacetophenone 4 (10 g, 50 mmol) and then 3 (10.6 g, 65 retool). The solution was
refluxed for 24 h, and after evaporation the residue taken up in CHCI 3 washed and the solvent
evaporated. The residue was stirred in CCI4"hexane (1.9) (50 mL) and filtered to give 9.4 g of 5
(74%), mp 75-76"C.
GOMBERG - BACHMANN - GRAEBE - ULLMANN Ap/iaton
Awl-awl bond formation via diazonlum salts Carbazole synthesis by intramolecular an/I-awl
bond format|on.
1 2 3 (S1%)
H H
1 Gomberg, M., Bachrnann, W E J Am Chem Soc 1924 42 2339
2 Smith, P.A..S
J Am. Chem Soc 1 951 73 2452,2626
3 Dermer, OC Chem. Rev. 1957 57 77
4 Graebe, C,UIIman, F Lzeblgs Ann. 1896 291 16
5 Ashton, BW. J Chem. Soc 1957 4559
6 Campbell, N. Chem. Rev 194 8 40 36O
2-(2'-N|b'ophanyl)thiophene (3).2 A cooled solution of 2-ntroaniline 1 (28 0 g, 0 2 rnol) m
water (80 mL) and HCI (45 mL), was diaZOtlZed with NaNO2 (14.5 g, 0.21 tool) m water (50
mL). The diazonium salt was fiitered and treated under cooling with thlophena 2 (500 g, 5.9
tool) and a solution of NaOAc.3H20 (80 g, 0 588 tool) zn water (200 mL) was added dropw=se
After stlrnng for 3 h at 5-10°C and for 24 h at 20°C, the organic layer and the Et20 extract of
the water layer were vacuum distilled to give 25 6 g of 3 (90%), bp 126-132oc (0.3-0.5 ram).
Redistdlaton and recrystaglzatlon from MeOH gave 21 0 g o(3 (51%), mp 51-52°C.

150 Name and Unnamed Reactions Name and Unnamed Reactions 151
G R I E C 0 Reagent
Pyndlnlum p-toluenesulfonate (PPTS) reagent I for protection of alcohols as the
tetrahydropyranyt ethers as well as for cleavage of ethers (in warm ethanol)
CH3"CH,-SO3H.HzO ч CsHsN  CH,4.SO 3 CSI.N* H
I
I CHzC
I Gneco, P.A J. Org. Chem 1977 42 3772
2 Pinmck, H.W. Tetrahedron Lett 1978 44 426t
Pyrldlnlum p-toluanesullonata (PPT$] (I]. I TsOH monohydrate (5 70 g, 30 retool)
was added to pyndine (12 I mL, 150 retool] with sllrnng at 20=C After 20 m|n the excess of
pyndlne was removed in vacuum (60oc) Recrystalhzaton from Me2CO gave 6 8 g o! I (90=/=),
mp t20oc
Geranlol tatrahydropyranyl ether (4). I Geranlol 2 (154 rag, I retool) and d=hydropyran
(126 rag, 1.6 retool) in dry CH2CI 2 (7 niL) contalning PPTS (25 rag, 0 1 retool] is stirred !or 4 h at
0°C Dilution wlth EI20, washing wdh bnne to remove the catalyst, evaporatlon of the solvent
and vacuum distdlatlon afforded 326 mg o! 3 (99%), bp 140°C/I0 ram.
Garanlol (2] A solution of 4 (! 19 rag, 0 5 retool) and PPTS (12 6 rng, 0 05 retool] in EtOH (4
mL) was sllrred at 55°C for 3 h Chromalography on silica gel afforded 77 mg of 2 (100=/=]
G R I E S S De.amlnation
Deaminaflon o! aromatic amines via diazonium salts, by moans of alcohols (Gdess), or
PO2H3, Sn(OH)2, etc.
 1 N='O2-HC 2 S r
NH2 
1 Gdess, P. Phil Trans. 18 64 154 683
2 Griess, p. Chem. Ber. 1897 21 547
3 Fletcher, T L. Synthesis 1 9 7 3 610
4 Komblum, N. Org. React. 1 9 4 4 2 262
1-Bromophenantrene (2). 3 2-Amlno-l-brornophenantrene 1 (0.8 g, 3 rnmof) was stirred with
THF (5 mL), 32% HCI (30 mL) and water (10 mL). Under stimng and cooling (5-10=C) a
solution of NaNO 2 (0.3 g, 4.5 mmol) in water (1 5 mL) was added dropwisa over 5 min. After
30 rain stirring at 0-5"C, 50% hypophosphorous acid (15 rnL) was added and the m=xture was
atirred at 0C for another 30 rain, then at room temperature for 17 h. Water was added and
the product collected and chromatographed on alumina, eluent Phil, then crystallized from
MeOH, to afford 0.5 g of 2 (66%), mp 109 5-110 5°C.

152 Name and Unnamed Reacnons
GRIGNARD Reagents
Organomagneslum reagent capable of reacting wdh active "H" compounds o in additions to C-X
bonds also nckel catalyzed couphng
1 21%1
+ NI (ll)
,,,%.,,e, tx  w,"/
o°ч tsuMgcl .__p ,-oH
1 Barbler, P CR 1899 128 110
2 Gngnard, V C R 1900 130 1322
3 IQmse W Synthesis 19 8 3 994
4 Sonntag NOV Chem Ray 1953 53 372
5 BogdanovK:hi, B Angew Chem 1983 95 749
6 Hayashi. T Chem Lett 1980 1209
7 Dubols, J F Ann Chum Fr 19 81 6 407
8 Walborsky HM Acc ChemRes 1990 23 286
8 Walhng, C Acc Chem Res 19 91 24 255
exo-2-Methylblcyclo(3 2.0]heptan-ndo-2-ol (2) 3 To MeM91 prepared from Mel (2 3 g, 16
retool) Mg turnings (0 4 g, 17 mmof) n Et20 (60 mL) was added bcycio [3 2 0] heptan.2.one 1 (11
9,15 mmol) n Et20 (10 mL) After 1 h reflux the mdure was hydroly-zed (25 mL water) and
extracted wth EI20 (2x25 mL) Evaporation gave 1 7 g of 2 (89%). punty 98% by GLC. purified by
preparative GLC (Carbowax + KOH 110°C), mp - 25°C
G U A R E $ K Y - T H O R P E Pyridone Synthesis
Synthesis of pyndones from beta dlketonas and activated amides
5 6 7 (65%)
1 Guaresky A Mere Real Accad Sc Tonno 1896 46 25(11)
2 Thorpe J F J Chem Soc 1 91 1 99 422
3 Katritzky AR Adv Heterocycl Chem 1953 I 347
4 Keliog, RM J Org Chem 1989 45 2856
3-Cyano-4,6-dlmethyl-2.pyrldona (7) 3 Pentane 2 4 done 5 (4 85 g 48 5 mmol),
cyanoacetamcle 6 (4 5 g, 53 mmol) and p|peridlne (2 mL) |n EtOH (50 mL) were heated to
reflux for 45 mln The product crystallized on COOl|rig Recrystallization from EIOH gave 5 5 4
g of 7 (63 68%) mp 298-300oc

154 Name and Unnamed Reactions Name and Unnamed Reactions 155
G U Y - L E M A I R E - G U E T T E Phenol Chlonnation
Regioselective ortho or para halogenation of phenols and the corresponding ethers (only para)
by hexachloro cyciohexadlene 2 or 3 respectively.
0 H - oH --.
""0
0 4
Cl CI  CI
Cl 
3 Cl 2 Cl Cl Cl
Cl
2 Guy, A,Lemmre, M,Guette, Jp Tetrahedron 1982 38 2339
3 Guy, A,Lemalre, M,Guette, Jp. Synthess 1982 1018
4 Guy, A., Lemalre, M., Guette, J.P. C.R. Acad. So. Set. 2
1 984 299 693
2,3,4,5,6,6-Hexachlorocyclohexa.2,4.dlene.l.one (3).2 To stirred CI 2 (0 3 tool) In
CCI4 (300 mL), was added sodium pentachiorophenoiate 1 (57 5 g, 0 2 rnol) at 0-PC After 3 h,
filtration and evaporation (below 40°C) left a residue This was stiwed in petroleum ether (200 mL)
at -10oC for 24 h and filtered to give 34 g of 2 (56%).
2,3,4,4,5,6-Hexachlorocyclohexa.2,5-dlene.l.one (2).2 Ci 2 was passed through a
suspension of AICI3 (5 g, 37 mrnol) in pentachiorophenol lot 4 h. After 48 h, filtration, evaporation
and recp/staiilzation from petroleum ether (200 mL) gave 28 g of 3
4-(4-Methoxyphenyl)-2.chiorophenol (5).2 To 4 (0.4 g, 2 mrnol) in 25% OMF in CH2CI2 (8
mL) was added 3 (0 6 g, 2 mmol). After 48 h at 20°C, workup gave 0.37 g of 5 (80%).
H A O O A O I N - I S S I O O R I O E S Ouinoxallne synthesis
Synthesis of qulnoxaline dioxKJes from benzolurazan oxKJe and ketone enolates or enamines (also
known as Beirut reaction).
O O  N -Ph
2 3, R. Ph-CO 
4, R:H 
48% 
1 Haddadin, M.J ,Issldondes, C H. Tetrahedron Left.
2 Issldoddes, C H, Haddadln, M J J Org Chem.
3 Haddadln, M J.,Issldondes, C H Tetrahedron
1965 3253
1966 31 4067
1974 30 659
4 Haddadin, M.J.,Issldondes, C H US Pat 4,343,942 ; CA 1984 101 171227
5 Lin, S K. YonliHuaxue 1991 11 106
2"Phenyl'3-benzoylqulnoxallne-N,N'-dloxlde(3). 2 A soiutlon of benzofurazan-N-oxlde 1 (3.4 g,
25 mmoi) and dibenzoylmethane 2 (5 6 g, 26 mmol) in warm Et3 N (25 mL) was allowed to stand at
20°C for 24 h. The mixture was diluted with Et3N, f'dtered to give 2.5 g of 3. The filtrate after
Standing another 30 h afforded a second crop of cr'/stalls. Total yield. 3.6 g of 3 (42%), mp 234oc
(from MeOH). Heating of I g of 3 m 45 mL of 2% KOH in MeOH unt,i ag dissolved gave 0 65 g
(95%) of 4, mp 205-206oc.

156 Name and Unnamed Reactions Name and Unnamed Reactiona 157
H A L L E R - B A U E R Ketone Cleavage
Cleavage of ketones, lacking a-hydrogen, with sodium amlde.
Ph  CH3
1 C 2 ()
1 Haller, A.,Bauer, E. C.R. 1909 148 127
2 Impastato, F.I. J.Am. Chem. Soc. 1962 84 4838
3 Paquette, L.A. J. Org. Chem. 1 98 8 53 704
4 Hamiin, K.F_ Org. React. 1957 9 1
1-Methyl-2,2-dlphenyicyclopropane (2).2 A mixture of NaNH 2 (3.0 g, 75 mmol) and 1-
benzoyi-l-methyl-2,2-diphenylcyciopropane 1 (9 3 g, 30 mmol) in PhMe (80 mL) was refluxed for5
h. The cooled reaction mixture was treated wth cracked ice (50 g) and the separated organic layer,
after washing with bdne was dist,lfed. The fraction bp 106.107C (2.5 mm) was collected. There
were obtained 4 9 g of 2 (79%).
H A N T S C H Pyndine Synthesis
One step synthesis of substituted pyrldinas from a beta ksto ester, an aldehyde and ammonia.
Hco
.c-c-o oBc-c. D .c" "- -CH
2 NH,, 2 4
1 Hantsch, A.
2 Phitltps, A.P.
3 Svetllk, J.
4 Eisner, U.
LJelg's Anno 1882215 172
J, Am. Chem. Soc. 1949 71 4003
J. Chem. Soc. Pefk.in l 1987 563
Chem. Rev. 1 9 7 2 72 1
3,5-Ol(ethoxyўarbonyl)-l,4-dlhydro-2,6.dlmethyl-4-(m-nltrophenyl) pyrldlne
(4).2 m-Nitrobenzaldehyde 1 (15.1 g, 0.1 tool), ethyl acetoacetate 2 (26.6 g, 0.22 tool) and
concentrated NH4OH 3 (8 mL) in EtOH (60 mL) was heated to reflux for 3 h. The hot sol.ion
was dllted wth water (40 mL), cooled, filtered, washed wdh 50% EtCH (10 mL) to give 16-18 g
Of 4 (43-48%), mp 166.187°C.

158 Name and Unnamed Reactions Name and Unnamed Reactions 159
H A S S - B E N O E R Cadonyf Synthesis
Aldehyde or ketone synthess by reaction of an alkyl halide with the sodium salt of 2-nitroalanas.
Me
"O-N'=CI, M e
Na ч ч  ---.-a-. ч C - N - OH
1 2 3
1 Hass, HB,Bender, ML. J. Am Chem. Soc. 1949 71 1767
2 Bersohn, M. J. Am. Chern. Soc. 1961 83 2136
3 Epsteln, WW Chern. Rev. 1967 67 247
2-Cyclohexenone (3).2 To a solut=on of sodium (782 mg, 34 mmo0, in MeOH (40 mL) was
added at room temperature, and under N 2 2-nitropmpane 1 (3.94 g, 44 mmo0 and then 3-
bromocyciohexene 2 (5 5 g, 34 mmoi). After 20 h, the solvent and cyclohexadiene were distilled
atm. pressure, the residue was treated wdh water and ether, the organic layer washed with 10%
solution of NaOH, and water After dn/ing over MgSO4, the solvent was evaporated and the residue
distilled "1 vacuum There was obtained 3 as a coiodass liquid, 1 43 g (44%)
H A S S N E R Azide azlddine synthesis
Stereospecific and regioseisctive addition of IN 3 (via Iodonlum ions) or of BrN 3 (ionic or tree
radical) to oieflne and conversicn of the adducts to aziddtnes or azidnes.
Ph ,,,,, ICI , LAH Ph
Na/j Me
1 ./...... := 2 (enthro) N H 3trans (95%)
N3 BrN 3 8rN3 N r
Ph,  Ph ,,,, Ph
pentane (tad) M ()
Br
1 Har, A. J Am. Ch. S. 1965 87 4203
2 Har, J. Am. Ch.S 1969 91 5046
3 Har, J. . Chem. 1968 33 2686
4 Hasher, A. J. Am. Chem . 1968 90 216
5 Har,  A. Chem. Res. 19 71 4 9
trans,2*Methyl-3-phenylazlrldlne (3). 2 To a slurry of 15 g (0.25 mole) of NaN3 .1 MeCN
(100 mL) below 0oc was added slowly 18 3 g (0 113 mole) of kine monochlonde over 15 mm.
After 10 min stirring, E-l-phenylpropene (0 1 mole) was added and the rrxture stirred at 20°C
overnight. The slurry was poured into 300 mL of cold 5% sodium thiosulfite and the orange oli
extracted with ether, washed wdh water (5x200 rnL), dned and evaporated. Flash chmrnato*
graphy (Woelrn neutral alumina, potroleurn ether) gave erythro 2 (100%). Not. Some S-
compounds react explosively wh IN3 To stirred LAH (2 5 g) in anh. ether (90 mL) was added
2 (10.3 g, 0.035 moI) in ether (15 mL) at 0°C over 20 rain Work up with 20% NaOH (10 rnL)
stirring, filtration, drying and evaporation gave 4.93 g (65%) of 3 and 5% of 1.

160 blame and Unnamed Reactions
Name and Unnamed Reactions 161
HASSNER "RUBOTTOM (x-Hydroxylatlon
(x-Hydroxylatfon, fodlnatfon, or oxlmation of cad:)onyls via silyl enol ethers.
CX?,OAr O
"  Ph OSIMe  Ph H
OH OAc
1 2 (85%) 3 (42%)
1 Hassner, A. J. Org. Chem. 1974 39 1785, 2556
2 Rubottom, G M. Tetrahedron Lett. 1974 167
3 Hassner, A. J. Org. Chem 1975 40 3427
4 Rubottom, G.M J. Org. Chem. 1979 44 1731
5 Ching-Kang, Sho J. Org. Chem 1987 52 3919
3-Phenyl-2-acetoxypropanol (3).3 To 3-phenyl-l-tdmethyls,lyloxypropene 1 (1 03 g, 5
mmol) in CH2Ci 2 was added slowly m-chioroperbenzoic acid (mCPBA) (1.1 g, 5 5 mmo0. After
h, aqueous Na2SO 3 was added. Work up gave 1 6 g of 2 (85%) e/lhro.'threo (7"3).
2 (2.12 g, 5.6 mmoi) in B20 (10 mL) was treated with Ac20 (1 mL), trlethylarnkle (2 mL) and 4-
pyrrolidlnopyddine (0.02 g) and the mixture stirred for 15 rain. MeOH was added to destroy
Ac20, the mdure was washed (NaHCO3,1.5 M HCI, water). Bulb-to-bulb distillation afforded
0 45 g o! 3 (42%), bp 110°C (0.15 torr).
HAUSER . BEAK OrthoLlthlatlon
Olho-alkylatlon of benzamldas.
o o obO
h h  o t-SuI.J
1
U b
2 h
1 Hauser, C R. J. Heterocycl Chem 19 6 9 6 475
2 Beak, P. J. Org Chem.
1977 42 1823
3 Hauser, C.R. J. Chem Eng. Data 19 7 8 23 183
4 Beak, P Acc. Chem Res 1982 15 306
5 Katntzky, A.R. Org. Prep &Proced Int. 1967 19 263
2-rI-BUtylbenzanlllde (3). 5 To benzanillde 1 (1 97 g, 10 mmoi) in THF (28 5 mL) and
HMPA (1.5 mL) was added 2 5 M n-t:xyllithlum (4 mL), dropwise at -70°C The mixture was
warmed to 20 ° and CO2 was passed through for 5 mln. After removal of the solvent under
vacuum, THF (30 mL) was added under Ar and at -70C 1 7 M ted butyllithium (8 5 mL), was
added slowly. The mixture was mataned for 20 mm at -20°C and recooled to -70"C. n-Butyt
Ixonde 2 (1.37 g, 10 mmol) was added A,'ter warming to 20 ° the mxture was stirred for a few
hours. The solvent was removed and 2N HCI was added to the residue at 0°C. The precipitate
was collected and recrystalllzed to gve 1 85 g of 3 (73%), mp 72-73°C.

162 Name and Unnamed Reactions
H A Y A S Y RealTangernent
RealTangement of o-banzoylbenzoic acids.
o o
1
2
1 Hayasy, M. J. Chem. So 1927 2516
2 Sandin, R.B. J.Am. Chem. Soc. 1955 78 3817
3 Caspar, M. L.
J. Org Chem. 1 968 33 2020
2"Methoxy'6(-2-chlorobenzoyl).benzolc acid (2).2 3"Methoxy-2(3-chlorobenzoyf).
benzoic acid 1 (1.0 g0 3.4 mmol) was heated in conc. H2SO4 (6 m.) for 1 h at 65oc. The cooled
reaction modure was poured into ice and neutralized. The cyciized product was filtered off (0 2 g)
and the filtrate was acidified to give 2, mp 205oc.
HELL - VOLHARDT - ZELINSKI Bromination
(pBmmination of carboxylic acids.
1 2 (%)
1 Hell, C. Chem. Ber. 1881 14 891
2 Vofhardt, J. Leblgs Ann 1887 242 141
3 Zelinsid, Y. Chem. Bet. 188 7 20 2O26
4 Gi)soI1, Th. J. Org. Chem. 1981 46 1003
5 Haworth, C. Chem. Rev. 19 6 2 62 99
Methyl 2-(1,S-Dlmethylbicyclo [2.1.1] hexanyl-2-bromoacetate) (2). 4 To a mixture of 1,5-
dimethylcycto [2.1.1] hexane-2-acelic acid 1 (2 92 g, 12.4 mmof) in PBr3 (7.94 g, 29.3 mmo
maintained for 1 h at room temperature, was added Br2 (7.94 g, 57 mmof) in two batches unde Ar.
The reaction mixture was heated on a steam bath for 3 h, cooled, quenched wth anh. MeOH,
diluted wth Et20 and the organic layer was washed with 5% NaHCO3 solution. Evaporation of the
solvertt and distillation of the residue gave 4.0 g of 2 (88%), bp 58-59°C (0.33 mm).

1(>4 blame and ]nnamed Reactio Name and Unnamed Reaction. 165
H E N B E S T Iddlum Reagent
Reagent for selective reduction of katones by means of an indium hydride.
HIClo
.... ° L.LJ
1 2
1 Henbeat, H B. J Chem. Soc. 1962 954
2 Bilcke, T.A. Proc. Chem. Soc. 1964 361
3 HIrschmann, H. J. Org. Chem. 1966 31 375
4 Hill, J. J. Chem. Soc. (C) 1967 783
5 Kid(, D M. J. Chem. Soc.(C) 1969 1653
5-a-Androstan-3a-hydroxy-17.one (2).5 A stock solution of reagent was prepared
from chioroiddlc acid (0.1 g), tdmelll phosphde (5 mL) and 2-propanol containing 10% water
(250 mL).
5(z-Androatane-3,17-dione 1 (20 mg, 0 07 mmol) was heated wilh $ ml. ol stock reagent
-olutlon for 94 h. The cooled mixture was poured Into water and extracted with
ather'benzene. The organic layer was washed wiIh water and NaHCO3 solution and the
soivenl was removed In vacuum to leave a crude product which contained 94% axial, 2%
equatonal alcohol and 3°/° unchanged 1. Pure 2 (axial OH) was obtained by chromatography
H E N R Y Nitro Condensaon
dol condensat|on of nltma(anes with aidehydes.
1 2 3
1 Henry, L. C.R. 1896 120 1265
2 Balker0R. J. Org. Chem. 1964 29 669
3 RostI,G. Synthesis 1983 1014
4 Hass, H.B. Chem. Rev. 1943 32 406
$ Lichtentafer, F.W Angew. CherlL Int. Ed. 1 96 4 3 211
1-Cyciohexyl-2-nitro-l-propanol (3). 3 To ice cooled nltmathane 1 (3.75 g, 50 mmoi) was
aided cyciohexylcarboxaldehyde 2 and the mixture was sllrred Ior 2-3 rain. Chromatographic
alurdna (Carlo FJba RS,  I accordng to Brockmann, 10 g) was added and stirdng was
ўonllnued for 1 h at room lemperature. After standing for 23 h, the alumina was washed with CH2Ci 2
(3x40 mL). The filtered extract was evaporated at reduced pressure Io give the crude 3. At a
l11peralure below 80C, unreacted 1 and 2 are distilled oil. Tllen the temperature is carefully
raed to afford 5 96 g of 3 (75%), bp 90-92C (0 6 mm).

166 Name and Unnamed Reactions
Name and Unnamed Reactions 167
HERBST . ENGEL . KNOOP . OESTERLING
Am|noacid Synthesis
,AJpha amino acids (and aldehydes) synthesis by reaction of an alpha kato acid with another amino
acid (Herbst-Engel) or by reaction of a keto acid with ammonia under redudng conditions (Knoop.
Oesteding).
NH2 C  I  ч CIHcCHO
O NH z
1 2 3 4
H(XX-CH z-CH Z--COOH NH,C;
 HOOC-CH =-CH rH.COOH
5 6
1 Herbst, R.M., Engei, W. J. Biol. Chero.
1934 107 505
2 Hedst, R.M. J.Am. Chero. So 1936 58 2239
3 Mix, H.
Z physiol. Chero. 1 961 325 106
4 Wieland Angew. Chero. 1942 55 147
5 Kncop, F, Oesteding, H. Z Chero. 1 9 2 5 148 294
6 Wleland Chero. Ber. 1944 77 34
Glulamic acid (6).6 2-Ketoglutarlc ac:J 5 (5.0 g, 36 mmoi), NH4CI (1.0 g, 20 mmoi) and NaOH
(0 5 g, 12 mmol) zn water (50 mL) was hydrogenated ,n the presence of P102. After 5 h the catalyst
was filtered and the product puntled by chromatography on alumina to give 6, mp 194°C.
H E R Z Benzothmzole Synthesis
Reaction of aromatic am,nes with sulfur mon<chlonde and an acyl chloride in the presence of
Zn salts to give 1,3-benzothmzoles
N NaOH .NHz 7JISO,I
c, ._,.o ,:,.o
1 2 (93%)
4 (3S%) 5 6
1 Her'z, R. Chero Zent. BI 1922 4 948
2 Herz, R U S Patent
1.637 023
3 Huestins, L.D J Org Chero 19 6 5 3O 2763
4 McChenard J Org Chero 19 8 4 49 1224
5 Warbudon, WK. Chero Rev 1967 57 1011
6-Chloro-2-phenyibenzothiazole (6). 3 1 (5 7 g, 0 045 moi) m AcOH (7 mL) was added to
$2CI2 (42. g, 0.31 moi; 25 mL) st,rred for 3 h at 25°C then for 3 h at 70-80°C The cooled
mixture was st,ITed with Phil (50 mL) and filtered to give 9 3 g (93%) of 2, mp 210-225°C
(dec). A vigorously stirred suspension of 2 (8 3 g, 37 mn'l) in ice-water (500 mL) was made
alkaline with 6N NaOH. Then NaHSO3 (5 0 g, 40 romol) was added and after 1 h heating, the
ml:dure was treated with Norlte and filtared To the solution of 3 was added excess ZSO4 to
precipitate the zinc mercaptide 4 (2 65 g, 38%) To a suspension of 4 (I 3 g, 3.4 romol) in
AcOH (40 mL) was added benzoyl chlodde 5 (2 0 g, 14 romol) After 30 rain reflux,
decomposition with water and cstalhzatlon from MeOH. gave 1 25 g o 6 (75%), mp 156-
157°C.

168
Name and Unnamed Reactions
H f L B E R T - J O H N S O N Nucleoslde Synthesis
Nucleoslde synthesis from bromosugars and methoxypydmldines (see Vorbmeggen).
3
1 Johnson, T.B. Science 1929 69 579
2 Hi3ert, G.E. J. Am. Chem. Soc. 1930 52 2001
3 Wolfram, P.H J. Org. Chem. 1965 30 3058
4 Uoricht, pL Angew Chem. 1962 74 767
2"Oxo-6"methoxy-3-(tetraacetyiglucosldo) pyrlmldine (3).2 Acetobromoglucose 1
(2-0g, 5 mmol)and2 (1.96g, 14 mmol)was heatedto 50eCfor 48 h The mixturewas tnturated
with water and 3-methyluracyl (1 g) separated. The residue solidit,ed upon addition of EI20 (5
mL), the Solid was filtered and washed with Et20 to remove unreacted 1. Two recstallizattons
from 50% F_tOll gave 0 5-0.7 g of 3 (23-32%), mp 220.221oc.
H I N S B E R G Thiophene synthesis
Synthesis of th,ophenes from z-diketones
c.c -- c. csHs
2 c c Hooc
C'zH3C" "S" "CCX3CzH s 3 (93%) zHs
1 Hinsberg, O Chem. Bet 191 0 42 901
2 Wynberg, N J. OrgChem 1964 29 1919
3 Wynberg, N.
J. Am Chem Soc
1965 87 1739
blame and Unnamed Reactions 169
H I N S B E R G - S T O L L Le Indole-Oxindole Synthesis
Indole synthesis from anilines and glyoxal (Hinsberg), oxindole synthe.us from anilines and
heloacyi halides (Stolie).
HO,,
.M. y, cH  M'°V-'. M,O ''''
• oso M M
1 2 3 4
Me
1 Hinsberg, O. Chem Bet lSS8 21 110
J Chem Soc 1932 546
2 Burton, H,
3 Stoll,R. Chem Bet 1913 46 3915
4 Slolid, R. J Prekt. Chem. 1930 128 1
5 Julian, P L. J Am. Chem. Soc 1 93 5 57 563,2026
6 Surnter, W. Chem Rev 1944 34 396
5,6-Olmethoxy-l-methyllndole (4). 2 Glyoxal sod, urn b,sulfite adduct 2 (32 g, 0.158 moo .1
water (250 mL) and 4-methylannoveratrole I (20 g, 0.12 moo "1 EtOH (150 mL) were refluxed
for 48 h The hot solution was filtered, cooled (0°C) and the sodium salt filtered to grve 19 g of
3 (63%), mp 187C 3 (5 g, 25 mmol) was refluxed in water'HCI (1 2) for 30 mln, filtered and
extracted with Et20; the soiut,on was baSlfied to give 4, mp 120-121°C.

170 Name and Unnamed Reactions
H I Y A M A Amlnoacrylate synthesis
Synthesis of 3-amtnoacrylic acids or derivatives from nitdles by atdol type condensation
1 Hiyama, T
2 Hlyama, T.
Tetrahedron Left. 19 8 2 23
1597
Tetrahedron Left. 19 8 3 24 3509
3 Hiyama, T. Bull. Chem SocJpn. 1967 60 2127,2131,2139
.jtuyl 3"=,A.m: .n o-_ 2- b ...... (2) .... D,isopropyl ..... (061g ..... ) ...........
ion o, '-IMgBr (4 3 mL, 3 mmoi) in Et20 at 0°C, and the mixture was stirred for 1 h t-
Bury1 acetate 1 (0.35 g, 3 mmoi) was added at 0oC and after 30 nun MeCN 2 (62 g, 1 5
mmol), and Ihe mixture allowed to react for 3 h at 0°C Quenching with NH4CI, extraction
with B20 and dist,liatlon gave 0 156 g of 3 (66%).
4,4"Dlmethoxy-3-amlno-2.pentenonitrlle (5).2 To a well stirred solution Of 2 (0.14 g. 10
retool), in THF (20 mL) was added dmpwise 1 6 moll. of BuLi (6 3 mL, 10 mmol) at .78oC
and stirdng continued for 15 m,n. 2,2-Oimathoxy propanndnis 4 (1 15 g, 10 mmol) was
added. Work up as above and racTstallizaton gave 1.26 g of 5 (81%).
Name and Unnamed Reactions 171
H I Y A M A - H E A T H C O C K Stereo,selective allylation
Stereoselective synthesB of anti i:llli(: alcohols by Cr promoted allylatlon of aldehydes.
o OH OH
1 2 3(75%)
I I'fiyama, T. J Am Chem. Soc 1977 99 3179
2 Heathcock, C H. J Am Chem Soc 1977 99 247, 8109
1978 1185
3 Heathcock, C H. Tetrahedron Lett.
4 Hiyama, T. Bull. Chem. Soc Jpn. 1982 55 562
5 Muizer, J. Angew Chem. InL Ed. 19 9 0 29 679
Anti - 4-Hydroxy-3-methyl-l-OCtene (3) 3 To a suspension of 3.7 g (23 mmol) of anhyd.
CrCI3 in 50 mL of THF at O°C, 440 mg (12 mmol) of LLAIH 4 is added in portions followed by
8.6 mmol o aldehyde 2. Cmty bromide 1 (2.32 g, 17.2 mrnol) in 50 mL of THF is added over
30 men. The mixture is stirred at 20"C for 2 h, poured into water and extracted with ether.
Removal of solvent gives 3 In 75% yield.

172 blame and Unnamed Reacuon
H O C H - C A M P B E L L Azlndlne Synthesis
Azlrldlnes from ox,mes or from a halo,mines (via az,nnes)
NH
H  (70%)
Ph
Ph
N Me Me
'CI LAH p N
I H H
1 2 (84%)
1 Hoch. J CR 1934 198
2 Carnpbe, KN J Org Chem 1943 8
3 DeKimpe N J Org Chem 1980 45 5319
4 Laurent A Bull Soc Chlm Fr 1973 2680
5 Kolera. K Tetrahedron 1968 24 3681 5677
Cls-l,2-dimethylo3-phenylazlridlne (2) 3 To a cooled and well strred suspensn of LAH (3 8
g. 0 1 tool) "1 EI20 (1O mL) was added dropwlse a solution of 2 2-dlchioro-N methyl
propicphenone ,m"1e I (10 8 g. 0 05 mol) .1B20 (100 mL) After ovem,ght reflux the rraxture
was poured with caution onto ice water and the product extracted with Et20 Evaporation of
the solvent gave 6 21 g of 2 (84%). bp 79 82oc
H O F M A N N Amlde Degradation
Degradation of amides to amines by means of hypohahdes
HCI 2 (95%)
1 Hofmann AW Chem Bet 1881 14 2725
2 Magnlen. E J Org Chem 19 58 23 2029
3 Applequlst Chem Rev 1954 54 1083
4 Cohen. L.A Angew Chem 1961 73 260
5 Wail,s. E S Org React 1948 3 268
1-Pentylamlne hydrochlorlde (2) 2 A suspension of caproamlde 1 (11 5 g. 0 1 tool) .1 NaOCI
solution was hested to 45°C under st,rang then at 75°C for I h and the product was stesm
dist,lled into excess of HCi Evaporation of the distillate left 11 7 g of 2 (hydrochlonde) (95%).
mp 137-139°C
H O F M A N N Ison,tnle Synthess
Isonltnle synthes,s from pnmary am,nes and d,chlorocarbene or dibromocarbene
1 2 R N*CH 3 (47%)
1 Hofmann AW LleblgsAnn 1868 146 107
2 Smlth. P.AS J Org Chem 1958 23 1599
3 Ugl JK Angew Chem Int Ed 1972 11 530
Ethyllsocyanlde (3) 2 To a solution of 33% 1 (40 mL 0 3 tool), benzyltnethylammon,um
chlonde (0 6 g) and NaOH (35 g 0 875 mol) was added dropwe bromoform 2 (50 3 g 0 2
moo The mixture was stirred for 24 h at 20°C and d,Stllled (1 and 3) Redlstlllation from KOH
gave 5 2 g of 3 (47%). bp 65"C

174 Name and Unnamed Reactions Name and Unnamed Reactions 175
H O F M A N N Elimination
Oleflns by elimination from quaternary ammonium salts (,less substituted olefin preferred).
I Hofmann, A.W. Chem. Ber. 1881 14 659
2 Hinskey, R.G. J. Org. Chem. 1984 29 3678
3 Cope, A.C. J. Org. Chem. 1885 30 2163
4 Francke, Angew. Chem. 1960 72 397
5 Brewster, J H. Org. React. 1953 7 137
6 Cope, A C Org. React. 19 60 11 317
3"(Dlmethylamlnomethyl)-2-methyl.6.heptene.2.ol (2).3 2-Methyl-5-
(dlmethylcarbinol)-N,N-dimethylpperldlnium iodide 1 (1.90 g, 10 mmol) was dissolved in
distilled water and treated with freshly prepared Ag20. The mixture was filtered atx:l
concentrated under vacuum to a synJp The residue was heated at about 150oc and 0.3 mm
and distilled to afford 0.85 g (75%) of 2, bp 50°C (0 5 mm).
H O F M A N N - L O E F F L E R - F R E Y T A G Pyrrolldlne Synthesis
Synthesis of pyrrolidines or pq:)endinas from N-haloamines (free radical reaction).
1 2
1 Hofmann, A.W. Chem. Ber 1883 16 558
2 Loftier, K., Freytag, C. Chem. Bet 1909 42 3427
3 K'nura, M. Synthesis 18 76 201
4 Wolff, ME Chem. Rev. 1963 63 55
Perhydrodlpyrldlno[1,2-a][l',2'-c]-pyrlmldlne (2). 3 (a) To an ice-cooled solution of
2-{2-(pipendyi)ethyl] pc)endine 1 (3.2 g, 10 2 mmol) in Et20 (200 mL) was added N-
chiomsucclnmide (NCS) (1.7 g, 12 7 mmol) Under stiffing, the reaction mixture was
Iwadated with a 300 W high pressure mercury lamp under N2 for 5 I1. The precipitate was
filtered, dryed and extracted with n-pentane Evaporation of the solvent and distillation gave
1.0 g of 2 (50%), bp 140°C (20 torr)
Co) To 1 (I.0 g, 5.1 mmol) and NCS (1 34 g, 10 mmol) in cooled B20 (200 mL) TEA (2.0 g, 20
retool) was added wzth stimng and irradiation as above Wodp gave 980 mg of 2 (100"/o).

176 Name and Unnamed Reactton, s Name and Unnamed Reacnons 177
HOFMANN'MARTfUS-REILLY.HICKIN BOTTO M
Aniline Rean'angement
Thermal or Lewis ac.,d catalyzed rearrangement of N alkylan,hnes to o (p-) alo/lated anilines
H .CI'L3 NH 2 CH 3 CH 3
+ Ph
1 2 (4. I H2N
1 Hofmann, A.W,Martlus CA. Chem Bet 1B71 4 742
2 Hart. H J Org Chem 1962 27 116
30gatta Y
Tetrahedron 1964 20 2717
4 Redly J,Hlcklnbottom, W j Chem Soc 1920 117 103
5 Cnpps R W J Chem Soc
1943 14
6 Fischer A J Org Chem 1960 25 463
o- and P'a-Phenetylanlllne (2) and (3) (a) By thermal rearrangement N a
Phenathylandlne 1 (hydrochlodde) (23 3 g 01 mol) was heated m a sealed tube at 200
230"C for 6 h The cooled mixture was exlraced with 15% HCI and EI20 The Et20 layer was
extracted with HCI The acid extract after neutrallzat,on Wllh 5% NaOH, extract,on with Phil
and dlshllaton gave 2 3 g of aniline and 4 2 g of 2 and 3 (24%), bp 165 170oC in a rat,o of 3 7
(b) By catalytic reaffangement A mixture cf 1 (19 7 g, 0 I mol) and ZnCI 2 (13 6 g 0 1 mol)
was heated in a sealed tube as above The same work gave up 3 6 g of aitlne and 6 8 g of 2
and 3 (41%). o p ratio 10"90
H O F F M A N - Y A M A M O T O Stereoselective allytatlons
Synthesis of syn or anti homoallylic alcohols from Z or E cmt,mnate and aldehydes
(Hoffman) or of syn homoallylic alcohols from crotylstannanes, BF 3 and aldehydes -
(Yamamoto)
0 c02e Pr OH
1 2  3 (90%) Me
"" SnBu Ph CHO BF3 
+  Ph
I Hoffman, RW Angw Chem Int Ed 1979 18 326
2 Hoffman, R W J Org Chem 19 81 48 1309
3 Yamamoto, Y J Am Chem Soc 1980 102 7107
4 YalT_moto, Y Aldnchmca Acta 19 8 7 20 45
5 Brown, HC J AmChemSoc 1985 107 2564
6 Roush. WR Teb'ahedron Lett 1988 29 5579
Homoallyl alcohol (3) 6 Metalahon of (E) butene (1 05 equw) wth n BuLl (t equw) and
KOtBu (1 equv) m THF at 50"C for 15 mm followed by treatment of (E)-cmtyl potassium salt
with B(OIPr)3 at 78°C gave after quenching with 1 N HCI and extraction with Et20 contalnlng
I equlv of dl, sopropyl tartarate, the crotyl boronate 2 A solut,on of decanal 1 (156 mg I
mmol) was added to a toluene soluhon of 2 (1 1 1 5 equw) (0 2 M) at -78°C contaJr, ng 4A
molecular sieves (15-20 mg/L) After 3 h at -78°1 N NaOH was added, followed by extraction
and chromatography to afford 208 mg of 3 (90%), anti syn 99 1

Name and Unnamed Reactions
H O L L E M A N N Pinacol Synlhesls
Dlmenzabon of ketones to 1,2-dols by means of Mg and other metals
Mg-Hg
2 pH-CO.CsH.C p 
Co CH,
1 2 (94%)
 .,  OH 
3
4 (93%)
1 Hol+n,M A F. R.Tr.Cm. 1906 25 206
2 GoIh, H. He'ta. 1965 48 1395
3 Corey, E J. J. . Chem.
1976 41 260
4 Zieann, H E. J. . Chem 1986 51 46044
4"Chlorobenzoplnacol (2).2 To magnesium tumlngs (2 5 g, 100 mat) and Iodine (9 0 g, 35
retool) in Phil (100 mL) and Et20 (30 mL) were added p-chlorobenzophenone 1 (10 62 g, 50
retool) with efficient stlrnng (exothermic). Alter 1 h, hydrolysis gave crude 2, whK;h was
digested with hot petroleum ether (30 n.) to afford 10.32 g of 2 (94%), mp 172-173oC (EIOH).
Cyclohexylpinacof (4).3 To HgCI 2 (0.044 g, 0.16 retool) in THF (3 mL) was added 70-80
mesh Mg (0 144 g, 6 at) and the mixture stirred under Ar for 15 rl'cn The supematant was
removed, the amalgam washed (THF) and THF (5 mL) was added At -10oC, TCI4 (330 L, 0 570
g, 3 r11ol) was added, followed by cycfohexanone 3 (0.196 g, 2 mmol) in THF and the purple
solution was stirred for 30 min at 0°C Quenching with 0.SM Na2CG3, extraction with Et20 and
evaporation of the solvent afforded 0.166 g of 4 (93%), mp 124-125oc
H O N Z L - R U D I N G E R Pephde Synthesis
Peptlde synthesis by coupling of acyl azldes with amino esters
N
R 10 R10
1
Ao NH- CH- C- NH- CH- CO- B
I R2 2
3
1 Honzl, l., Rudinger, I. Coil Czech Chem. Comm. 1961 26 2333
2 Slebel, F Helv. Chlm. Acta. 1970 53 2134
3 Medzihradsky, K Acta Chlm. Acad. ScL Hung.1962 30 105
4 (3ndetti, MA. J. Am. Chem Soc. 1965 90 4711
5 Klausner, Y.S Synthess 1974 554
General procedure for azlde coupling. 5 Protected peptlde hydrazlde I (26 mmol) in
DMF (84 mL) at -20°C was treated wth 3.35N NCI in dloxan (70 mmol), t-Butyl nitnte (3 85 mL)
(or NaNO2 in water) was added at -15°C and the mixture was maintained at -10°C for 10
The amino component 2 (18 mmol) in DMF (320 rnL) was added dropwlse at -15°C, then
ethyldilsOpropylamine (70 mmol) and the mxture kept at 0°C for 24 h. During the first 6 h, 0.5
mL of the base was added ever hour Finally the product 3 was precipitated in K;e-cold 1%
AcOH (1B00 mL).

180 Name and Unnamed Reacnon, s
H O R N E R - K N O W L E S - K A G A N Asymmetric Hydrogenation
Enantosalectlve hydrogenation of prochlral olefins with chlral Rh catalysts
Et
ph,,,J + RhCI (hexadlene)2 + Ph P'-Pr HZ H Me
1 2 (S) 3
 NHCOMo RhCI (ўyclooct e n e  H...= P h "'*" COl
O p /
CO2H (  Ph2 8 NHCOMe
4 "oPPh2 (R) 6 (90%) 81=/@ ee
I Homer L Angew Chem Int Ed 1 968 7 942
2 Knowles, WS J Chem Soc Chem Commun 1968 1445
3 Kagan H B J Am Chem Soc
1972 94 6429
4 Kagan, HB J OrganomeLChem 1975 91 105
(S)'(+)-2-Phenylbutane (3).1 The catalyst 2 was obtained by adding [Rh (1.5-
hexadlene)CI]2 (0 5xi0 "4 moles) in Phil (20 mL) to (S)-(+) methylpherlyl.-n-pmpylphosphme
(2 2x10 "4 moles) under H 2 ,',-Ethylstyrene 1 (10 2 moles) was injected The reactmn took 6-8
h (by GC) Chromatography on AI203 gave 3 (7.8% ee)
N'Acstyl'.(R)-phenylalanlne (6).3 The dod.um catalyst was obtained by adding (-) dlop 5
(from dlethyl tartrate) to a benzene solution of [RhCl(cyciooctene)2] 2 under At. and stlrdng for
15 mm A solution of the Rh catalyst (I mM in BOH Phil 4 1) was introduced under H 2 to a
soluhon of z-N acalylamlno--phenylacrylic acid 4 (molar raho Rh 4 - 1.540) The solvent was
evaporated, the residue dissolved In 0 5 N NaOH. the catalyst was filtered and the solution
acidified and concentrated to dn/nass to give 6 (81% ee) in 90 95% yield
HORNER - WADSWORTH - EMMONS Olefmallon
Wittlg type reaction of phosphonate stabilized carbanlons with aldehydes or ketones to form
olefins
j I! II NaH
(MeO)2-P-CH2C  
o  c;o - .--.,....,...,,
2 1 OAc 3 (87%) °
I Homer L Chem Bet 1958 83 733
2 Wadsworlh, W S, Emmons W D J Am Chem Soc 19 6 1 83 1733
3 Berkowltz WF J Org Chem 1882 47 824
4 Tamlzawa T K Synthess 887
1985
5 Sampson C R J Org Chem 1986 52 2525
6 Tsuge, 0 Buff Chem Soc Jpn 1987 60 4091
7 Boutagy, J Chem Revs 1974 79 87
Unsaturated ketone (3) 2 To a suspension of Nail (21 4 mg 0 883 mmol) in DME (4 mL),
under N 2 was injected a solution of d methyl 2.-oxoheptylphosphonate 1 (210 mg. 0 95 mmol)
in DME (1 mL) After strnng for I h (voluminous preoptate) and ice cooling aldehyde 2 (100
rag, 0 442 mmol) in DME (I mL) was mlected Stlmng was continued for 30 rmn under ce
cooling followed by 2 5 h at 20o(3 The mudure was neutralized with AcOH (0 12 mL) and
concentrated Chromatography on slrca gel (45 g) and eluton with EtOAc hexane 1 I, gave
125 mg of 3 (87%)

182 Name and Unnamed Reaction Name and Unnamed Reactions 183
H O U B E N - H O E $ C H Phenol Acylation
Synthesis of ketones (or aldehydes) by acylahon of phenols with nltrdes (or ortho formates)
NO J H/ZnC2 h
1 2 3 (2s%) O
Me],OH Me OH
+ HC(CE=)2  CHO
1 Houben, J. ChemBer. 1913 46 2447
2 Hoesch, K. Chem. Ber 19r15 48 1122
3 Trucare, J. J. Org. Chem.
1963 28 3206
4 Roger, R Chem. Rev. 1961 61 184
5 Spoen'i, P E. Org. React. 1 949 5 387
6 Gross, H. Chem. Bet. 1 963 96 308
6"(Phenylacetyl)dlhydro-.tubanll (3).3 A solution of dihydro--tubanll 1 (0 8 g, 4 5
mmol), phenyfacetonitn'le 2 (0 8 g, 7 mmol) and ZnCI 2 (2.5 g) in Et20 (28 mL) and CHCI 3 (13
mL) was treated with dry HCI for 10 min under COOling and stirring. The mixture was allowed to
stand at 25oc ovemight, the Et20 layer was decanted and the oily residue was treated with
alkali and heated on a water bath for 2 h. Exlracflon with Et20, washing the extract with 5%
NaOH and evaporation of the solvent gave a residue which was recrystallized from
Et20:pontane to give 0.38 g of 3 (28%), mp 81-83"C.
HUNSDIECKER - BORODIN - CRISTOL - FIRTH
Decarboxylatlon - Bromination
Substitution of carboxylic groups by halogen va Ag salts (Hunsdlecker, Borodin) or Hg salts
(CnstoI-Firth)
I 2 (69"/.) 
CH-COOH + B= HgO h
P CI-CsH4-Br
3 4 (80%)
I Borodin, A LleblgsAnn 1861 119 121
2 Hunsdiecker, HC. Chem Ber. 1942 75 291
3 Luh, Tien-YanLuh J Org Chem. 1981 49 5328
4 Johnson, RG. Chem Rev. 1956 56 219
5 Wilson, CV Org React. 1957 9 332
6 Cristol, S J., Firth, W C J. Org Chem 19 61 26 280
7 Meyers, A.J J Org Chem. 197 9 44 3405
4-Chlorobromobenzene (4). 7 A suspension of I>.chlorobenzoic acid 3 (1.56 g, 10 mmol)
and HgO (3.25 g, 15 mmol) In CCI4 (50 mL) was heated to reflux and irradiated with an 100
W bulb. Br 2 (2.40 g, 15 mmol) was added via syringe and the mixture heated and irradiated
for 3 h. 5% NaHCO3 (30 mL) was added and the mixture stirred vigorously for 15 rain Work
up and distillation gave 1.53 g of 4 (80%), mp 66-68,C.

184 Name and Unnamed Reactions Name and Unnamed Reacnons 185
I M A M O T O Cerium alkylatlon
Cenum mediated or samarium mediated alkylaton of ketones and aldehydes in the presence
of esters; see also Kagan-Mofander.
CH,--'-CH,--CH21 + CHa--CaH4..  P Br-CaH4---CH2-CH=CH ,
4 $ S (77%)
1 Imamolo, T J Chem. Soc. Chem. Commun. 1984 163
2 Imamolo, T. J Org Chem 198 4 49 3904
3 Imamoto, T. Tetrahedron Lett. 1985 .26 4763
4 Imamoto, T TetrahedronLett 1986 .27 3243
4-Hydroxy-4-(p-bromophenyl)-l.pentana (3)2 Ce lumlngs (280 rag, 2 at) were Irealed with
HgCI 2 (250 rag, 0 9 rnmol) in EtOH (2 mL) for 2 mln under Ar The solvent was removed and
the residue washed with Et(H and dned in vacuum To lhe Ce amalgam was added allyl
iodide I (336 mg, 2 retool) in THF (3 mL) and 2 (700 mg, 2rnmol) under Ar at 0"C. After
reaction, lhe mixture was Irealed with aq. NH4CI and extracled wth CHCI 3 Evaporation and
preparabve TLC (silica gel) gave 45g mg of 3 (95%).
2"Cyclopropyl-l-iodo-2.propanol (6). To freshly scraped samanum powder (300 rag, 2 al) at
0"C was added a few drops of a SOlution of 4 (84 rag, 1 retool) and 5 (803 rag, 3 mmof), in
THF (6 mL). After imtation, lhe rest was added with stirring dunng 20 rain, end after 20 Inn a!
0"C, the rrllxture was treated with 1 N HCI and extracted with ether. The combined extracls
were washed with aq Na2S203 solution and bnne, and dned over MgSO4 Evaporation and
preparatNe TLC gave 175 mg of 6 (77%)
I S A Y Ptendlne Synthesis
Synthesis of ptendines from diamlnopyflmldlnes and a-dlkatones or a--ketoaldehydes.
0 H:zN N H '-'--""
+ H N NH N N H
a , N NI.
1 2 3 (41%)
1 Isay, Chem. Ber 1908 39 250
2 Shaman, R.x J. Org. Chem. 1 971 36 3925
3 Albell, A. QuarL Rev. Chem Soc. 1 g 4 9 2077
2-Amlno-4.-hydroxy.6-phenylpteddlne (3), 2 A suspension of 2,4,5-tdamino-6-
hydroxypydmdine sulphate 2 (2 9 g, 8 4 retool) in water (30 mL) was treated wdh BaCI2, 2H20
(2.0 g, 8.4 mmol), and after 10 rain stlmng was filtered. The pH of the filtrate was adjusted to
4 0 wth Na(Ac, phenyl glyoxai 1 (1.1 g, 8 2 mmol) in Me(H (10 mL) was added and the
mixture was heated on a steam bath for 3 h. The precipitate was dissolved in IM NaC)H and
reprecipltated by 10M Na(H. By neutrahzatlon with AcOH and drying in hgh vacuum one
obtains 0.85 g of 3 (41%), Zmax (0.1M Na(H): 270 rap.

186 Name and Unnamed Reactions Name and Unnamed Reactions 187
J A C 0 B S E N Reermngement
Nkyl group mlgr'ion in aroma systems.
SC H Me
ME Me ME SO,j H
1 Jacobsen, C. Chem. Ber. 1866 19 1209
2 Smlthe, Li. J. Am. Chem. Soc. 1946 7O 2209
3 MawelI, E.N. J. Org. Chem. 1965 30 4014
4 Smith, LI. Org. React. 19 4 2 I 371
5,6-Dlmethyltetralln (2).2 A mixture of 6,7-dlmethyltetralln I (18.0 0, 0.11 mol) and
H2SO4 was heated under stirring to 80°C and maintained at this temperature for 15 min, then
at 25°C for 24 h. The mixture was diluted wdh water and (stilled with supedleated steam.
Flora the distillate by extraction with Et20 and distillation there was obtained 4.5 g of 2 (24%),
bp 110-115oc, nD = 1.5530.
J A P P Oxazole Synthesis
Oxazole synthesis from benzoin and ndriles or ammonium formate.
Ph "CH--OH Ph = N
phC:O Ph
1 2 3 (3O%)
n-Pr-,CH._OH n-Pr N
n.Pr 'C-'O (s1%)
I Japp, F.R. JChem. Soc. 1893 63 469
2 Bredereck, H.I. Chem. Ber. 1954 87 726
3 Willey, R.H. Chem.Rev 1945 37 420
4,5.Dlphenyloxazole (3). I A mixture of benzoin 1 (30 0 g, 0.14 mol) and KCN 2 (60 0 g,
0 9 mol) was added to conc. H2,SO4 (800 mL) under strring and cooling (CAREI HCN is
formed). After a few hours at 25°C the mixture was poured into water, the oily product was
heated with Na2CO 3 and extracted with Phil. Vacuum distdlatlon afforded 9.0 g of 3 (30%),
bp 192.195oc.

188 Name and Ummmed Reacttons 189
J A P P - K L I N G E M A N N Hydrazone Synthesm
Synthesis of hydrazones flom dlazonlum salts and an activated methylene group (or
enamlne)
1 2 3 (s2%)
1 JaPP, FR,KIIngemann, F CeBer 1887 2O 2492
2 Frank, RL Jn Cem So 1949 71 2804
3 Jackman, A. Chem Commun. 19 6 7 456
4 PNIIIps, R.R. Org React. 1959 10 143
5 Robinson, R Chem Rev 1 9 6 9 69 233
2-Formylpyrldlne p-nltrophenylhydrazone (3).2 Ethyl 2-pyndylacetate 1 (I,06 g, 63
retool) was stirred for 3 h wdh KOH (0 4 g, 70 mmol) m water (15 mL), then diluted wdh water
(10 mL) and acidified with HCI Dlazonum salt 2 (from p-nitroanlllne 0 869 g 6.3 mmol and
NaNO2 (0 434 g, 6 3 retool) was added foflowed by a cotd solution of NaAc (2 0 g, 24 mmol)
mwater (4 mL) and kept for 20 h at 0-5°C Filtration gave 1 25 g of 3 (82%), mp 231-234oc
JAROUSSE . MAKOSZA Phase transfer
Phase transfer (PT) catalysis by quatemary ammonlJm salts of substation, addition,
cartnyl formation, oxidation, reduction
CHrCOH2CCOCH + CH I R4 N* H$O4
1 2 CH,, 3 (80%)
1 Jalousse, MI CR set C 1951 232 1424
2 Makosza, M Rocz Chem 1965 39 1977
3 Dockx, J Synthesis 1973 411
4 Weber, WP Angew Chem Int Ed 1972 11 530
5 Dehmlow, E V
Angew Chem Int Ed 1974 13 170
6 Hams, JM J Org Chem 1985 50 5230
7 Wang, JX J Org Chem 1986 51 275
Methyt acetopropanoate (3) 3 (C alkylabon) Tetrabutylammon=um hydrogen sulfate (lOT
catalyst) (34 6 g, 0 I rnol) and NaOH (8 0 g, 0 2 mol) in water (75 mL) was added to well
stirred 1 (11 6 g, 0 1 tool) and Mel 2 (28 4 g, 0 2 tool) in CHCI3 (75 mL) The reaction is
exothermc and becomes neutral after a few rain The CHCI 3 layer was evaporated Et20
was added to filter the PT calalyst Evaporation of Ihe Et20 gave a mixture of 3 (80%)
(monoalkylated) and 20% dlalkylated product
Phenyl butyl ether 6 (O alkylatlon) Phenol 4 (9 4 g, 0 I rnol) and butyl bromide 5 (27 4 g,
0 2 mol) were stirred with NaOH (6 0 g, 0 15 rnol) n water (500 mL) in the presence of PT
catalyst (1-10 mrnol) After all phenol was consumed, usual work up gave 13 5 g of 6
(90%), bp 210-211oc, n = I 4970

190 Name and Unnamed Reactions
Name and Unnamed Reacnons
J E G E R Tetrahydmfuran synthass
Free radical ring closure of alcohols w Pb(AcO)4 to tetrahydmfurans
1 cs 2 (62%) 4
trans2 (7%)
-H
I Jeger, O Heir Chlm Acta 1959 42 1124
2 MICOVlC, VN Tetrahedron 1984 20 2279
3 Moon Sung J. (gig Chem 1989 34 288
4 Michalioviol, M L Synthesis
1 970 209
cls'7-Oxablcyclo[4,3,0]nonane (2).3 A mixture of 2 cyciohexylethanoi I (10 g, 78 mmol)
and lead tetraacetate (60 g, 135 mmol) .1 Phil (100 mL) was refluxed for 19 h The mixture was
fered, the filtrate washed (H20, NaHCO3), the solvent evaporated and the rescue dmtllled In
vacuum to gwe 6 19 g of 2 (62%), bp 39-62C/I 5 mm Byproducts identified by GC trans 7-
oxabioyclo[4,3,0]octane (7%) and 2-cyclohexylethyl acetate (30%)
J O H N $ O N Phenol alkynylatlon
A base induced rearrangement by conversion of al tri- Or tetra-haloethyl ethers Into o-
hydroxyphenylalkyne$ and into helen)cyclic systems
OH O-CFICHCI, Q " OH
1 2 (90%) 3 (80%)
Me Me
C)CH 3 OCH=
3
1 Johnson, F J Org Chem
1985 50 5430
2 Johnson, F J Oig Chem 1986 51 5040
1,1-DlfiuOro.2,2-dlchlorOelhyl aryl ether (2) Phenol 1 (4 7 g, 50 mmol) was dissolved
In  KOH (14 mL) and 40% Bu4N+OH - (2 mL) To this solution at 0°C was added 1,1-
dlchlom-2,2-dlfluoroethylene (9 98 g, 75 mmol) and CH2CI 2 (35 mL) and shaken vigorously at
25°C for 16 h Isolation afforded 10 56 g (90%) of 2
2-Hydroxyphenyl lrlmethylsllyl acetylene (3). 4 The ether 2 (2 39 g, 10 mmol) in THF
(30 mL) at -78°C under N 2 was treated wth n BuLl (41 mmol, 20 mL of 2 molar solution) in
hexane over 20 rain with stlrnng Alter overnight heating to 20°C, quenching in Me3SICI (1 mL),
treating with petroleum ether and filtration, the solvent was evaporated and the residue
chmmatographed (petmlaum ether EtOAc 9 I) to afford I 52 g of 3 (80%)

192 Name and Unnamed Reacnons Name and Unnamed Reacnons 193
J O N E S Oxidation Reagent
0xldatlon of alcohoLs to aldehydes or ketonas with CrO3-H2SO4 in acetone
Ph- CH- C,-CH C.-H..S O,=
O
1 2 (68%)
OH O
CFIjO " CH=O
°1 o-
Jones, ERH J Chem Soc 1946 39
Dauben, WC J Org Chem 1980 45 4413
Phenyl ethynyl ketone (2), 1 To a stirred sofutlon of phenyl ethynyl carblnol 1 (342 g, 2 59
mol), in Ue-CO (500 mL) was added slowly a solution of CK)3 (175 g, 1.75 mol), in water (500
m(.) and 98% H2SO4 (158 mL) under N 2 at +5'C in 4-5 It .ater stirring for a further 30 rain, the
mixture was diluted with water and the product extracted with Et20, Evaporation of the solvent
and recstallizatton of the resKJe from Me(H H2( afforded 258 g of 2 (68%), mp 50-51oc
J U L I A - B R U Y L A N T S Cyclopropyl Calnol Rearrangement
Synthesis of allyl halK:les (usually E) by rearrangement of cyctopropyl carbinols
catalyzed)
OH
1
I Bruylants, P Bull Acad Royale Beige 19 28 28 160
2 Julia, M Bull Soc Chum Fr 196 0 1072
3 Juris, M Bull Soc Chlm Fr 1961 1849
4 Ju6a, M Tetrahedron Suppl 1966 443
5 Koclenscky, P J Chem & Ind 1 961 549
6 Nakamum, H Tetrahedron Left 1973 111
Trans 1-Bromo-2-pentene (2) 3 Methyt cyclopropyl carblnol 1 (43 5 g, 0 5 mot) was stirred at
room temperature with 48% HBr (20O mL) for 10-15 rren After extraction with petloleum ether
(40-60C) and washing the extract with NaHCO3 solution, the solvent was removed in vecuum
and the re=due distilled to gNe 52 g of 2 (8O%), bp 125-126°C (757 ram) or 68.-69°C (102
ram), n = 1 4683

194 Name and Unnamed Reactions
Name and Unnamed Reactions 195
JUNG . OLAH . YORONKOY Ethercleavae
Cleavage of ethers or esters, cadamates, pho'ohonates with lImethylsilyl iodides.
Deoxygenatk)n of suitoxides.
 PhCOle.j  ph CO2H
1 2 3 3a (8S%)
4
6
1 Jung, M.E. J.Am. Chem. Soc. 1977 99 968
2 Jung, M.E. J. Org. Chem. 1977 42 3761
30ah, G.A. Angew. Chem. lnL Ed. 1976 15 774
40lah, GI Synthesis
1977 581
5 Jung, M.E. Chem. Commun
1978 315
60lah, G. Tetrahedron 1962 38 2225
7 Voronkov, M.G.
Zh.Obshch.Khlm. 1976 46 1908
Benzoic enid (3a). Methyl benzoate 1 (136 rng, 1 retool) tdmetl/Isilyl iodide 2 (0.16 mL, 1 2
retool) in CC4 (0.5 mL) was heated to 50oc for 35 h. (NMR yleid of 3100%). The reaction
mxtore was stin'ed with 10% NaHCO3 (10 mL) for 30 rain. Acidification of the aq. layer and
extraction with Et20 ' folk)wed by evaporation of the solvent afforded 104 mg of 3a (95%), mp
118-| 19,C.
CYr.Johexanol (6a). A mixture of cyclohexyl methyl ether 4 (1.722 g, 15.1 retool), 2 (3.5 mL,
24 mmol), pyndine (0.5 mL, 6 retool) in CHCI 3 (4 mL) was heated at 60oc for 64 h. Quenching
wire MeOH (2 mL), extractk)n with Et20 ' firatJon of pyddine.HCI, concenVaUon of the filtrate
and chromatography (silica gel 70 g, eluent Et20) gave 1.274 g of 5a (84%).
K A B E Chromanone synthesis
Synthesis of 4-chromanones by condensation of sallcylaldehydes or o-hydroxyaryl ketones
with enamines or ketones.
1 2 3
H'jC r y 'OH +
CH=
1 Kale, H.J. Oebgs Ann
2 Kale, H.J Synthesis
3 Kale, H.J Synthes;s
4 Kelly, S E. J. Org. Chem.
CH
HC
1976511 511
19 78 887
1 978 888
1991 56 1325
2-Splro-4-chromanone (3). 2 A mixture of 2-hydroxyacetophenone 1 (600 g, 4.4 rnol)
and pyrrolidinocyck)pentene 2 (630 g, 4 6 tool) ;n MeOH (1000 mL) was refluxed for 2 h
After work up the product, distilled under vacuum, afforded 770 g of 3 (86%), bp 100-
105C/0.05 ton', mp 38-39°C.

196 Name and Unnamed Reactwns
Name cmd Unnamed Reactwns 197
KAGAN-MOLANDER Samarium reagen(
Lanthande reagents , speclcally samarium, Ior generation of free radicals useful In cyCllZatlons,
reductions
Sm + I.CH2.CH,r I  S12 O OTs OH
o
 OH (75%)
I
' ; (74%:
o.. o
o- ,.,-0 THF 2O °
1 Kagan HB JAlChem Soc 1980 102 2693
2 Kagan HB Tetrahedron 1986 42 6573
3 Motander G A J Org Chem 1 988 51 2598
4 Molander G A J Org Chem 1 9 91 56 4112
§ Soderqulst, J A A/dncheca Acta 1 9 91 24 15
6 Molander, G A. ChenRev 1992 92 29
7 I-lanesslan S Tetrahedron Left 1 992 33 573
Samarium dliodide (3) 1 Sm I (3 g, 20mmol) In THF (250 mL) treeted wdh 1 2-dKxJoethane
2 or CH212 gave a 4x10 "2 M blue-green solution of 3
2,2,9,9-Tetramethylbicycio(3 3 1)nonen-1.-ol (6). 4 To Sml 2 3 (18 8 mL, 1 88 mmol) in
THF was added Iron tnedibenzoylmethane (12 8 mg, 0 018 mrnole) in THF (15 mL) Iodoketone
4(272mg 0845 mmolnTHF(10rnl_)waseddedat.78ocin5min After2hstlmngat0oC the
modum was quenched wdh sat NaHCO3 (9 ml.) Flash chromatography (pentane - EJ20 ) and
subhmatlon afforded 122 mg (74%) of 5 mp 16g-172oc
K A I S E R - J O H N S O N - M I D D L E T O N Dindnle cycllzatlon
Synthesis of heterocycles by cycllzatlon of dintrdes by means of HBr
' --'----
 Br NH 2 CN
1 2 (6o%)
3 r
1 Johnson F J Org Chem 1962 27 2241 2473 3953
2 Kaiser A M Roemer J J U S Patent 1 9 5 3 2 630 433 2 658 893
3 Mlddleton WJ J Am Chem Soc 1958 80 2822 2B32
4 Johnson F J Org Chem 1 964 29 153
2-Amlno-6-bromopyrldlne (2) 1 Glutaconondrle 1 (12 5 g 27 retool) was added dropwlse
to a solution of HBr in AcOH (30 g of 30%) n 5 rain wdh cooling and Stilling The yellow
preclpdale after hltratlon and washing (NaHCO3 sol) was extracled wth EI20 and recnstalhzed
from Et20 petroleum ether to give 2 7 g of 2 (60%) mp 88 89°C
3"Amlno'l"bromo-6,7,8,9-tetrahydro-4H-2-benzazeplne(4) s 2( Cyanoethyl) 1
cyano cyciohexene 3 (1 2 g 7 5 mmol) in Et20 was treated wth a stream of HBr for 15 rain at 0°C
The solvent was removed in vacuum and the residue recrystalhzed from Me2CO Et20 to give
0 9 g of 4 HBr mp 212 214°C (MeOH Et20) 4 mp 150 155°C (CH2CI2)

198 Name and Unnamed Reactions
K A K I S Rean'angernent
Formation of ketones by bromlnaton - rearrangement of substituted ethylenes.
PhzC==CPhz + Br 2 Ag"
 PhC  CPh.j
1 0
2 (94%)
I Kak,s, FJ J Org Chem 1971 36 4117
2 Fet,zon, M J. OrgChem 1973 38 1733
Phenyl Tdtyl ketone (2). 1 A solution of tetraphenylethylene 1 (3 3 g, 10 retool) in CHCI 3
(250 rnL) COOled in an ice bath was saturated with CI 2 until a distlnc yellow color was present
The stirred mudure was treated with a 9 1 solution MeOH H20 saturated with AgNO3 and the
stzmng was continjed at 20oc for 20 h. The Inorganic salts were filtered off and the filtrate
diluted wth water The °rganic layer was separated, washed and dned (MgSO4) and the
solvent was removed zn vacuum to give a residue which crystaihzed spontaneously One
obtains 3 27 g of 2 (94%), mp 183.164oc.
K A L U Z A Isothiocyanate synthesis
Formation of isothiocyanates from amines.
cs, o" ccoEt
P*CI'C1H4-NH2  Ar-NH- C-S"  Et s ------.-.i,- p*CI-CeH,r..-N = C - S
EtN  H Et N, O*
1 2 3 GO'A,)
1 Kaluza, H. Monatsh. 1912 33 363
2 Hodgkins, JE. J. Org. Chern. 1956 21 404
3 Hodgkins, JE. JAm. Chern. Soc. 1961 83 2532
4 Hodgkins, JE. J. OrgChern. 1964 29 3098
K A M E T A N I Amine oxidation
Ox:t=on of primary amines 1o ndnlos by Cu(I)CI - 02 - pyndme
p-Methoxybenzonltrlle 2. p-Methoxybenzylamlne 1 (0 137 g, 1 mmol), 4 A molecular
sieves (8 g), and Cu2CI 2 (0.6 Cu(I) equiv ) in dry wddlne (50 rnL) were stJn'ed at 60'C for 4 h
under 02 atmosphere. More Cu catalyst was added and the reaction continued 20 h. The
n'axture was poured on ice (100 g) and 36% HCI (60 mL) and extracted with CH2CI 2 (3x50 mL)
The extract was washed (NaHCO3), dned and evaporated to give 0.131 g ol 2 (99%), mp 61oc

200 Name and Unnamed Reactions
K E I N A N Silane Reagent
Dliodosllane (DIS) reagent for mild hydrolysis of ketals, acotals or reducllve Iodlnatlon of
ketones and aldehydes.
0
8" " -----"-'--""
r 1 .42", 1 mm Br
2 (99%)
4
 ""OH (94%) + ! (2%)
1 Keman, E. J. Org. Chem. 1 987 52 4846
2 Kelnan, E. J. Org. Chem. 1990 55 2927
2 Keinan, E. Synthesis. 199 0 6a 1
p'Bromoacetophenone (2).2 Ketal 1 (625 rag, 2.58 mmol) in CH2CI 2 under N 2 at -42C
was treated with DIS (73 rng, 0.26 retool) and Stirred for I min. NaHCO3 (1 rnl.) was added
wdh vigorous stimng and the mixture allowed to warm up to 20oc The organic layer was
washed wth Na2S203 (5 rnL) and dried over MgSO4. Evaporation of the solvent and
chromatography (s|l'ica gel -CH2CI2) afforded 510 mg of 2 (99%).
Benzyl Iodide (4)2 DIS (420 mg, 1 5 mmol) was added to 3 (105.2 rag, 10 retool} in
CH2CI2 (5 mL). The mixture was stirred for 5 mln at 20C and quenched wdh 10%
aqueous NaHCO3 (0 5 mL) and 10% Na2S203 (0 5 mL), diluted wdh CH2CI 2 (20 mL), and
washed Wllh water. The organic phase was evaporated and the residue in CH2CI 2 filtered
through silica gel. Evaporation afforded 210 rng of 4 (96%).
Name and Unnamed Reactions
K H A N D - P A U S O N Cyciopentenone Annulatlon
Cyclopentenone synthess from cad)on monoxide acelylene and oleflns, coball carbonyl
> HCICH. co 
" coa (co)l  0
1 2 (74%)
1 Khand, J.U.,Pauson, P.L.J. Chem. SoPertun 1973 977
2 Pauson, P.L. Tetrahedron
1985 41 5855
3 Schore, N.S. J Org. Chem 1 987 52 569
3 Schore, N.S. J. Org. Chem.
1988 53 203
4 Schore, N.S. Org. React. 1 9 91 40 1
Endo 3a,4,5,6,7,Ta-Hexahydro-4,7-methano-2.1ndene.l.one (2).1 A solution ol
octacad:xnyldcoball (I .0 g, 3 retool) and blcycio [2 2.1] hept-2-ene I (3.0 g, 32 mmol) in
Iscoctane (100 rnL) was stirred first with acelylene and then under a mixture of 1.1 of acelylene
and cadmn monoxyde at 60-70°C until gas absolT)tion ceased (total 1550 mL). The mixture was
concentrated and the residue chromatographed on neutral alumina. Petroleum ether Phil
(1:1) eluted acelylene hexacarbonyl dicoball 70 rng, Phil CHCI 3 (1.1) eluted a yellow oil which
after disUIlation afforded 3 54 gof 2 (74%), bp 101-102oc (15 ram) Coiodess crjstals from
pentane, mp 32C.

202 Name and Unnamed Reactions
Name and Unnamed Reactions
KHARASH . SOSNOVSKY AJlylicOxidatlon
Allylic or propargylic oxidation wth t-butyl peresters.
St--C=c-st + ph_l.O.O_.Su Cua
--.--.-..m- E!--C mC- ICO..CO Ph
1 Kharash, M. Sosnovky, G. J. Am. Chem. Soc.
2 dulla, M.
Tetrahedron Lelt.
3 Kropp, H.
Synthesis
1 9 58 80 756
1976 2141
1 9 77 894
2"Benzoyloxy-3.hexyne (3).3 Peroxybenzolc aod t-butyl ester 2 (5.83 g, 30 mmol), Cu(I)
chlonde (10 rag) and 3-hexyne 1 (8 5 g, 130 retool) was heated for 14 h at t40oC. The COOled
reaction rrcxture was diluted with Et20 (20 rnL), and the orgar, c extract was washed with Tntlplex
Solution (2x25 mL). Evaporation of the Solvent afforded 3 5 g of 3 (57%), bp 75-78oc (0 04 ram)
K I L t A N I - F f S C H E R Sugar Homologation
Synthesis of Cn+l sugars from Cn sugars
H-=O
I I lH,oH
CH  OH CH  OH
1 2 (100") 3
1 Kllani, H. Chem Bet 1885 18 3066
2 Fischer, E. Chem. Ber 1889 22 22O4
3 Wood, H.B. J. Org Chem 19 61 26 1969
4 MowP/,DT. Chem. Rev 1948 42 239
3-Deoxy-D-rlbohexose (3). 3 To a frozen solubon of KCN (2 01 g, 41 mrnol) and NaOH (1 49 g,
37 mmol) in water (186 mL), was added a SolutK)n of 2-deoxy-D-nbose 1 (5 0 g, 37 retool) n 0 2M
NaHCO3 (186 n'd.) and the mixture was strred at 20oc unt,i homogeneous After 16 h (negative
Fehing test) the Solution was deonzzed on Ambedde IR-120-H +, concentrated zn vacuum and
predpitated wth Me2CO (25 mE) to gwe 6 87 g of 2 (100%),
(z2. +23.1.
A Solution of 2 (1.1 g, 6 8 retool) In water (50 mE) and sodium aad oxaiate (2 0 g) was cooled to
and under stlrdng was treated wth NaBH4 (0 5 g, 13 mmol) n water (10 mL). The pH ol the solution
was maintained at 4.5-5. Nter dilution with MeOH to preopltate the salts, the Solution was
delor, zed by Ambedlte IR-120-H + and Duolite A-4 and the concentrate was treated with anhydrous
EtOH. After several days at +5°C, crystals were filtered, 0.42 g (38%), mp 102-104°C Pure 3 Irom
EtOH,
mp 105-106"C, (z) U = +32  (H20)

204 Name and Unnamed Reacnons
K I S H N E R Cyclopropane Synthess
Cyclopropanes from unsaturated carbonyl compounds vm wrazohnes by cataiytK: pyrolysis
Ph CH.CH CHO + N..j.H20 ------.)=.- ph.N. N
H
1 2
3 (37%)
S (/.)
1 Kshner N J Russ Phys Chem Soc 1911 43 1132
2 Jeger O Heir Chum Acta
1949 32 1817
3 Hammond. G S J Am Chem Soc 19 S4 76 4081
4 VanAuken, TV JAm Chem Soc 1962 84 3736
5 Crawford R J Can J Chem 1974 54 4033
5"Phenyl'A2°pyraz°llne (3). 3 Cmnamaldehyde 1 (30 g, 0 227 rno/) and hydrazlne hydrate 2
(15 mL, 0 3 mol) m EtOH (60 mL) was refined for 4 h The solvent was evaporated and the
residue distilled in vacuum under N 2 The first fraction, bp 120"CJ14 mm, was clnnamaidehyde
followed by a fraction with bp 142-146"CJ14 mm This fraction on redlsffltatlon gave 12 g of 3
(37%), bp 138-139"CJ12 ran1, nl) 5 ., 1 5695, mp 41-42"C plcrate mp 107-107
Phenylcyclopropene (5--).3 3 (118 g 0 8 moO, powdered KOH (30 g, 0 53 roof) and platm=zed
asbestos (2 5 g) were heated slowly and the heat was shut off et the first sign of reactmn
After the exothermc reaction the temperature was again raised and the product was ddled
Both the distdlate end the residue ware steam distilled, the dstitlate was extracted with Et20 '
the solvent evaporated end the residue distilled to give 11 5 g of S (12%) bp 173 5"C (740
mm), n., 1 5320
Name and Unnamed Reacnons 205
KNOEVENAGEL . DOEBNER . STOBBE Condensation
Base catalyzed aldol condensation of aldehydes or ketones with an activated methylene group
of a malonlc ester (Knoevenagel Doebner) or a sUCClnlc ester (SIobbe)
 ....... :::1 ....  ....
OCH.j OCH= OCH s OCH 3
1 2 3 (95%)
Ph H z COOEt Nail Ph\
"C=O +  C.--- C -- COOE
Ph' CH z -COOEr 20"C ph / I
CH2COOEt
4 5 6 (97%) s
I Knoevenagel, E Chem Ber 1896 29 172
2 Doebner, O Chem Bet 1900 33 2140
3 Rapoport H J Org Chem 1981 46 5064
4 Grayson DH J Chem ,Soc. Perknl 1986 2137
5 Emden D
Chem Bet 1987 120 2717
6 Jones, G Org React 1967 15 204
7 Stobbe H Chem Bet
1893 26 2312
8 DaubGR JAmChemSoc 1946 70 418
9 Martelly.J Tetrahedron 1974 30 3063
10 Johnson, W S Org React 1951 6 1

206 Name and Unnamed Reacaons Name cmd Unnamed Reactions 207
K N O R R Pyrazole Synthesis
Pyrazole synthese from a -o"ўarbonyl compound and a hydmzne.
2 3
1 Knott, L. Chem. Ber. 1 8B3 16 2587
2 Mosley, MS. J Chem Soc 1957 3gg7
3 Katntzky, A.R. Tetrahedron 1964 20 29g
3-(3,5-Dimethylpyrazol-4'-yl)pentane-2,4.dlone (3).2 To a stirred suspension of
diacatyl hexanedione 1 (2.0 g, 10 mmol) in boiling EtOH (50 mL) was added hydrazlne hydrate 2
(0.6 mL). The clarified (charcoal) hot solution was evaporated in vacuum alld the oily residue was
crystalhzed from water to afford 0.9 g of 3 (46%), mp 134-140"C.
K N O R R Quinoline Synthesis
Quinoline synthesis by cyclization of acetoacatanllides.
75"95 H
2 (9O%) 2
1 Knorr, L LiebigsAnn 1886236 69
2 Hodgkinson, A. J. C:)rg. Chem. 19 6 9 34 1709
3 Bergstrom, F.W. ChemRev. 1944 35 157
4 Bergstrorn, FW. ChenRev. 1946 48 47
K N U N Y A N T $ Fluoroalkylatlon
Fluoroaikylatlon of aromahcs using hexafluoroacatone
1 2 3 {94%1
4 2 5 IS7"/,)
1 Knunyants, lL z.Vses Chlm Obsh. 1960 4 114
2 Simmons, H.E J. Am. Chem Soc. 1960 82 2288
3 GIIbed, E E J Org. Chem. 1 965 30 998,1001
4 Knunyants. I.L. zl.AkadNau/cSSSR 1962 4 682
Bis(Trifluoromethyi)phenylcarbinol (3).3 To a suspension of AICI3 (5.0 g, 37 mmol) n Phil
1 (880 g, 11.3 tool) cooled externally, was bubbled hexafluoroacetone 2 (bp -28'C) until it was
absorbed. 115 g, 6 72 mol (ca 6 h). The reactK:>n rn0dum was washed, dried and dlstgled to g/re
541 g of 3 (g4%).
P'Aminophenyl-bis(trifiuoromethyl)cerbinoi (5). Aniline 4 (93.1 g, 1 mot) was heated at
170"C and 2 (175 g, 1.05 mot) was bubbled in over 2 h. The mixture was heated to 170-180"C for
30 rain. The cooled mixture was dissolved in Et20 and petroleum ether was added. After
concentration, there are obtained a first crop of 131 g of 5 (50%), mp 148-150°C. The mother iquor
gave 45 g of 5 (17%), mp 80.100"C.

208 Name and Unnamed Reacnons
Name and Unnamed Reactions 209
K O C H I Cross Coupling
Cross coupling of organometalfcs wdh organic halidas catalyzed by ,'on (lit).
F(OBM b
Ph- IVlgBr + BCH,,CHoPh 
Ph-CH-CH-Ph
1 2 3
 + B,M o5 FC
4 6 6
1 Kochl, J. Synfhesl$ 1971 303
2 Kochi, J. J. Org. Chem. 1975 40 S99
3 KochI, J. J. Org. Chem. 1976 41 502
4 Molander, G.A. Tetrahedron Lett. 1983 24 5449
F(DBM)3 Catalyst. 3 To an aqueous solullon of FeCI3 (0.6 g) was added a solution of
dtberlzoyl methane (DBM) (1.85 g, 2.76 mmol) in BOIL After addition of NH4OH the solid was
filtered, washed, tided and recrystalF,d from Phil-petroleum ether, 70% yield, mp 270oc, ;mcx
Trarll Stllberre (3).2 A solulion of catalyst Fe(DBM) 3 (0.15 reel) in THF was added to
PhMgB 1 (45 mmof) in THF. After 5 rain atkdng, a solution of I-bromeslyrene (12 retool) In THF
was added (ice bath). The mixture was stirred for 1 h, flllered and concentrated to 50%. The
solution was exlracted with S% HCI and the solvent removed in vacuum to give 3.
K ) E N I G S - K N 0 R R Glycosldatlon
Synthesis of glycosides from bromosugars n the presence of Ag + or Hg 2+
M HO
H OH v-
3 (11"/o)
1 K6enigs, W., Knorr, E. ChemSer. 1901 34 957
2 Ice, C.H. ,/.Am Chem. Soc 1952 74 4606
3 Knochel, A. Tetrahedron Lett 1 974 551
4 Israel, M. J Med. Chem. 1 9 8 2 28
3-O-.L.RhamnopyranosyI-D-glucose (3). 2 A mixture ol 1,2,5,6-dl-0-isopropyhdene--
D--glucoturanose 2 (0.6,2 3 mmol), bromorhamnose 1 (0.66 g. 1.9 mmol) and Hg(AcC)) 2 (0 25
g) in dry Phil (10 mL.), was shaken for 4 days at r L The mixture was washed wth water, distilled
to dryness and the residue (0.55 g) was rred with 0.1 N MeONa (0.5 mL) in MeOH (4 mL) fo 6
h. The solution was neutrellZed wl|h oxalic acid, the solvent removed in vacuum and the resclue
heated with 0.01 N oxalic aad (10 mL) at 100°C Ior 3 h. The cooled solution was treated 
BaCO3., filtered and the filtrate delor, zed by Ambedqe IR-100H and IR-4B ion exchange resin.
Paper chromatography on Watman 3MM (n-BuOH.AcOH.H20 12.3 5) atlorded 62 rng of 3
(11%), F 0.92.

210 Name and Unnamed Reactions
K O H L E R Isoxazole-N-oxlde Synthesis
Synthesis of 2-isoxazole-2-oxldes from 1,3-dinroallranes or !-halo-3.rltro alP, aries.
Ph
Ph-CH 2 ...... --,  -- PhN,oPh
h Ph
1 2 3 4 (52%)
1 Kohisr, E.P. J.Am. Chem. Soc. 1924 46 2105
2 Nlelsen, A.T. J. Org. Chem. 1969 3, 984
3 SITUth, LI. CherrLRev. 1938 23 255
trans'3,4,5"Trlphenyl-2-oxazollne.2.oxlde (4).2 Phenyfnltromethane 1 (27.4 g, 0 2
tool) and benzaidehyde 2 (10.6 g, 0.1 tool) were mixed wdh methylarnine hydrochlodde (0.1 g),
K2CO3 (0 05 g) and EIOH (1 rnl.). After a week at 20°C, the soiven( was evaporated and Phil
added; the mixture was maintained at 25=C for 4 days. The solutJon was concentrated to a small
voluma and filtration gave cis-a-nltrostllbene 5.0 g (22%). The filtrate was evaporated to
dness and triturated with EtOH to give 4.5 g of 3 (12%), mp 174.178oc.
A solution of 3 (0 15 g, 0.4 mmol) rn MeOH (5 mL) containing NaOMe (0.2 g) was refluxed 3 nn,
cooled and me Solid flllered off. Recl/stallllzatlon from MeOH gave 65 mg of 4 (52%), mp
163oc.
Name and Unnamed Reactions
KOLBE Elec'olysls
Electrochemical decarboxylatton-dimerizatton (via free radicals).
2 Ph2CH-CC(: electrolysis_ ph2CH  CHP,n2
DMF, 17h -
1 2 (24%) 3
1 Kolbe, H. LiebigsAnn. 1849 69 257
2 Crum Brown, A., Waker, A. Proc. Roy. Soc. Edinburgh 1 8 9 0 17 292
3 Finkeistein, Mo J. Org. Chern. 1969 25 156
4 Rabson, M. J. Org. Chem. 1 9 61 46 4082
5 Man:luet, B. Bull. Soc, Ctwn. Ft. 1 988 571
8 Vi]h,A.K. Chern. Rev. 1967 67 625
7 Schaefer, H.J. Angew. Chem. Int. Ed 1 9 81 20 911
1,1,2,2-Tetraphenylethane (2). 3 A Solution of diphenylacetic acid 1 (21 15 g, 0.1 tool)
in DMF was electrolyzed for 17 h and the vollage was increased from 120 to 220 V dunng
electrolysis. The reaction mixture was poured into water and extracted with Et20. The extract
was filtered, washed and the solvent evaporated. Recrystalllzatfon from CHCI 3 gave 4 g of 2
(24%), mp 207-208°C.

212
Name and Unnamed Reaction,
Name and Unnamed Reactions
K O L B E - $ C H M I D T Salicylic Acid Synthesis
Carboxylahon (usually ortho ) of phenols, fndusthal melhod to oblain saticyl'ў acid derivahves
CH COH
2 (4.)
1 Koibe, H. lJeblgs Ann. 1860 113 125
2 Schmlo't,R Jprakt. Chem. 1885 31 397
3 Doub, L. J Org. Chem. 1958 23 1422
4 Lindsey, A.S Chem. Rev 1967 57 583
5 Raecke, B Angew. Chem.
1958 70 t
60a,K. Bu/I. Chem Soc Jpn. 1974 47 2343
P-Aminosal|cylic acid (2).3 A suspension of m-aminopher 1 (131 g, 0.12 mo) and KHC03
(30.0 g, 0 3 tool) in water was heated under CO 2 pressure at 90-95oc for 4 days The mixture was
coed to O"C and after filtration was acied strongly with conc HCL The prec.,pdaled 2.HCI (12 8
g, 56%) was treated with water (20 mL) and dissolved by addihon of KHCO3. The soMon (60 mL)
was decolozed by NaHSO 3 and charcoal and after filtration was acidified with 50% H3PO4 ' cooled
to OC, and the product was filtered, washed, and dned to give 8.0 g of 2 (48%), mp 160-162oc
K O N A K A Oxidizing Reagent
Oxidation of alcohols to cafooxyflc acids (or ketones) with nickel peroxide
I Konaka J Org. Chem 1962 27 1660
2 Konaka J.(rg. Chem 1969 34 1334
Nickel peroxide (1). 1 A mixture of 6"/,, NaOCI (300 mL) and Na(::)H (42 0 g, 1 rnol) was added
dmpwlse to a solution of NiSO4 6H20 (130 g, 0 5 tool) in water (300 mL) and stirred at 20°C for
30 rain. The black nickel peroxide was filtered, washed and dned in vacuum
Benzoic acid (3). A solution of benzyl alcohol 2 (2 16 g, 20 mmol) and Na(::)H (1 0 g, 25
retool) in water (50 mL) was lreated wth I (18 0 g, I 5 equlv) under stlmng at 30°C. After 3 h the
solution was filtered and the hltrale was acidified The precipitate was collected and dned to
afford 2.1 g of 3 (86%), mp 122 5°C

214 Name and Unnamed Reactions blame and Unnamed Reacdon 215
K  N I G Benzoxazine Synthesis
Benzoxazne synthesis from quinones.
o 1 HHBr 2  l• 3
1 Konig, KH Chem. Ber 1959 92 257
Z. Anal. Chem.
2 Konlg, K.H 1959 166 92
3 Flemming, J Z. Phys. Chem.(Lezg) 1964223 106
4 Day, JH. J. Org. Chem. 1965 30 4107
5 McMudrey, K.D. J. Org. Chem. 1 970 35 4252
3,4-Olhydro-4-methyl-2H-1,4-benzoxazlne-6-ol (4). s To a solution el 1,4-
benzoquinone 1 (30 0 g, 0.277 mol) and 2-1:'omoethylmethylamme hydrobromde 2 (30 0 g,
0.137 moo in 5(P/,, water- MeOH (2000 mL) at 0C, was added dropwse 0 2 N NaOH (500 mL).
Alter 2 h the mixture was liitered and the soad washed with water and tnturated with Me2CO
The acetone soluble fraction afforded 6 g of 3 (18%), mp 140-144°C
A solution of 3 (1.0 g, 4 retool) in CHCI 3 (100 mL) was shaken with aqueous soum dithlonle
until the organic layer became colorless. The glassy residue oblalned after evaporation was
dissolved in dxane:TEA (1.1) (100 mL) by heating 12 h on a steam bath. Evaporation and
chromatography (preparative TLC - Phil MeOH 9:1) gave 0.6 g of 4 (89%), mp 77-78 3'C.
K O R N B L U M Aldehyde Synthesis
Synthesis of aldehydes from pnma alkyl ha,des or tosylatas, using dimethyl sulfoxlde (DMSO).
OMSO
p Br-CeH4-CO-CHr : p Br-CH4,O-CHO
1 2 (91%)
 I Ag T$ R - T$ DMSO
:  CHO
3 4 (7o%)
1 Komblum, N. J. Am Chem. Soc. 1957 79 6562
2 Komblum, N. JAm. Chem. Soc. 1959 81 4113
p-Bromophenylglyoxal (2). 1 p-Bromophenacyl bromide 1 (15 96 g, 57 retool) in DMSO
(100 mL) was stirred at 20 ° for 9 h, poured into water and extracted with Et20. Evapora,on of
the solvent and recystallization of the residue from n Bu-O-Et afforded 11.2 g of 2 (91%), mp
123-124°C.
I'laptanal (4). 2 To silver tosylate (11 0 g, 38 retool) in MeCN (100 mL) were added n-
Indoheptane 3(7 0 g, 30 mmol). The mixture protected from light was maintained 24 h at 20 o,
poured on ice, the product was extracted with Et20 and the residue after removal of the solvent,
was poured into Na2CO3 (20 g) In DMSO (150 mL). Alter heating 5 rain at 150°C under N 2, the
aldehyde was separated as its 2,4-dindrophenylhydrazone (DNPH) to afford 6.9 g of 4 DNPH
(70%), mp 106-107"C.

216 Name and Unnamed Reactions blame and Unnamed Reactwns 217
K O $ E R Tosylation
Vic-bis tosyla,on of alkenes by means of hydmxytosyloxyiodobenzane.
1 Koser, G.F. J. Org. Chem. 1977 42 1476
2 Nelland, O J. Org. Chem. USSR(Engl.) 1970 6 689
3 Koser, G.F. J. Org. Chem. 1980 45 1542
4 Koser, G.F. J. Org. Chero. 1884 49 2462
ErythrO(dl)-2,3-bla(tosyloxy)pentane (3).4 A mixture of hydroxy(Iosyloxy)-
Iodobenzene 1 (3.92 g, 10 retool), cis 2-pentene 2 (2.5 mL, 1.6 g, 23 retool) and CH2CI2 (20
mL) was allowed to stand for 28 h at 3oc, to give a yellow soluOon containing a floating scum.
This was washed with water (2x20 mL), dried (Na2SO4) and concenVated under vacuuro. The
oily residue atter washing with pentane (15 mL) and reTstallizatlon from a mixture of MeOH (6
mL) and pentane (3 mL) at -20oC gave 827 rng of 3 (40%), mp 82-83oc. A second crop from the
mother liquor raised the yield to 44%.
K R I E F - R E I C H Oleflnation
Synthesis of olefins by stereospecio reductive eliromatlon of -hydmxyalkyl selanides (a
variant of Peterson ok)flnatk)n) by means of MeSC2CI, HCIO4 or P214 .
C(CH ,CH  CH- (CH)sC HC,, C(CH= CH----. CH-
1 OH SePh ether, 25' 2 (85%)
OH MeSOC
4 3 5 (71"/.1 6191"/.)
1 Knef, A. AngewChero. Int. Ed. 1974 13 B04
2 Reich, J.R. J. Chem. Soc. Chero. Commun. 1 975 790
3 Kdef, A. Tetrahedron Let. 1976 1385
4 Reich, J.R. J Am. Chero. Soc 1 979 101 6638
5 Knof, A. Bull. Soc Chsm. Ft. 1 9 9 0 681
Tatradec.7-ene (2). 3 1 (125 rng, 0 34 romol) zn 2 mL of ether was stilted with an atheral
extract of "P/;, HCIO4 (0 4 mL, 0.14 retool). After complaton (TCL) the mixture was poured into
aq. NaHCO3 (10 mL), extracted wdh Et20, dned and punfled by preparative TLC (SiO2 Merck,
pentane) to gwe 2 (85%).
1.Methylene.4.tert.butylcyclohexane (6). 4 To Is(phenylseleno)methane 3 (783
rag, 2.4 retool) in THF (5 mL) at -78°C under N 2 was added n BuI.J (2.4 retool). After 10 rain 4
(309 rng, 2 retool) in THF (1 mL) was added and after 5 nn water (10 mL) and after 5 rain the
mixture was poured into water and hexane ether 1 1 (15 mL). After distillation of mathyt
Phenyl selenlde, butyl phenyl selen,::le and 4, cnJde 5 (2"8 rm,xture of diastereomers), was
crystallized from 5% Et20-hexane to yield 144 rng of 5 (71%), mp 68 5-70°C, and a 2rid and
3rd crop. 5 (309 rag, 0 951 m111ol) in CH2CI2 was treated with TEA (480 rng, 4.76 retool) and
MeSO2CI (326 rng, 2.85 retool) to yield of 6 (91% by NMR).

218 Name and Unnamed Reacnons Name and Unnamed React=ons 219
KR)HNKE - ORTOLEVA PyndumSlts
Formation of keto pyndlnlum sslts by reaction of alpha halo ketone derivatives with pyndlne and
cJeavaga to cadx)xў acis
1 Krohnke, F ChemBer 1933 66 604
20doleva, G GazzCh/m./ta/ 1899 25/ 503
3 King I C J Am Chem Soc
1944 66 8941612
4 Krohnke, F Angew Chem Int Ed 1983 2 380
5 Aivarez, S I
Tetrahedmn 1 986 42 699
I-Naphtoic Acid (4). 1 1 and pyndlne 2 were heated on a water bath for a shorl time The
product was dissolved in EtOH and precipitated with Et20 Recrystaillzatlon from 10 volumes of
water afforded pure cz-naphthacyl pyrldlnlum bromide 3 A solution of 3 (0 5 g 1 5 mmol) in waler
(40 mE), EtOH (12 mE) and 10 N NaOH (2 mL) after heating for 12 mm on a water bath, gave on
acldlfP..ation and extraction with Et20 4 mp 160-162oc
1-Phenacylpyridlnlum Iodide (6) 5 Iodine (25 0 g, 0 1 mol) was added to acetophenone 5
(12 0 g 0 1 mol) and 2 (25 mE) heated at 95°C for 30 rain and at 20°C Ovem|ght Excess 2 was
removed and 6 (InSoluble in water or EtOH) was separated from pyndlnlum hydrolOdlde
KUCHEROV - DENIGES Hydration
Water eddition to a triple bond (Kuchemv) to a double bond (Oen=ges) under mercury salt
catalysis
5 6
1 Kucherov, M Chem Bet 1881 14 1540
2 Thomes, RJ J Am Chem Soc 1938 60 718
3 Denlges, G Bull Soc Chlm Fr 1898 19 494(3)
4 Shearer, DJ Can J Chem 1955 33 1002
5 AI-zoumenlan, N Synthesis 1971 527
2-Hxanon (2) 2 To H2.SO4 (1 0 g 10 mmol), HgSO4 (1 0 g, 3 3 mmol), 70% MeOH (150 g),
70% Me2CO (150 g) and 60% AcOH (50 g) at 60°C + 10C 1 (41 0 g, 0 5 mol) was added
under stlmng for 1 h Work up after heating for 3 h gave 30-35 g of 2 (60-70%), bp 127°C
1,2-Dlhydroxy-2.-methyl-1 phenylpropane (4). 5 To a suspension of HgO (21 7 g, 0 1 mol) in
1N H2SO 4 (200 mL 0 2 mol) was added 2 methyl-1 phenylpropene 3 (6 61 g, 50 mmol) The
mixture was shaken for 2 days filtered and the resK:fue washed with MeOH and Et20 The
filtrate was extracted with Et2 O and CHCI3 and the solvent was evapodaed to yield 5 8 g of 4
(70%) mp 54-62°C, mp 63-63 5°C after crystallization from Et20-petroleum ether

220 Name and Unnamed Reactions
Name and Unnamed Reacnons 221
K U H N . W I N T E R S T E I N Olefinatlon
Olefin formation from glycols by means of P214
HCIC HO
l-Cmmc o
o
1 hn, R, Wlemtemn,  He tm  19 28 11 87
2 hn, R,meein, A HelmA 1955 27 309
3 Inffen, C
Lleblgs Ann 19 65 684 24
3'4"BIs(4,ethylenedloxocyclohexyl).exene.l,dllne (2)3 P2 14 (60 g, 0 135
 w e h CS 2  a xhle To Ih e was  3,s(4,
etlhel)'3,hexi= 1 (30 g, 0 0  In pyi ( mL) 
m w sfl  2C r 2 h a  m was sBl e mse was trt wdh
EI  er  the Pwas mtra on Wlm Aina, a II
Ragatn from MeOH aflo 12 9 g  2 ()
K U M A D A - F L E M I N G Stereoselechve hydroxylatlon
Stereoselectlve conversion of alkyl s|lanes to alcohols
SMe2Ph OH
Ph HOAc Ph
1 2
R 'Me2Ph R H
R2 R2
X=ON
1 Kumada M Tamao K Tetrahedron 1983 39 983
2 Kumada M Tamao K J Org Chem 1983 48 2120
3 Fleming, I J Chem Soc Chem Commun 1 984 29
4 Kumada M Tamao K TetrahedronLett 1984 25 321
5 Flerrmg, i
Tetrahedron Lett 1987 28 4229
6 Fuchs PL TetrahedronLett 1991 31 7513
($R,RS)-4-Hydroxy-3-methyl-4-phenylbutan.2.one (2) 5 To a st|fred
Metaiaton of (E) butene (1 05 equlv) with n BuL (1 equw) and KOtBu (1 equ|v) in THF at
for 15 mln followed by treatment of (E)-crotyl potassium salt wh B(OiPr)3 at 78=C gave after
quenching with 1 N HCI and extractn with Et20 conta=nlng 1 equ|v of dilsopropyl tadarate the
Crolyl boronate 2 A solution of decanal 1 (156 mg 1 retool) was added to a toluene solution ol
2 (1 1 1 5 equlv) (0 2 M) at 78°C conta|ning 4A molecular sieves (15 20 moJL) After 3 h at
78°1 N NaOH was added Iollowed by extraction and chromatography to afford 208 mg of 3
(90%) ant, syn 991

222 Name and Unnamed Reactions Name and Unnamed Reactwns 223
K U M A D A - N E G I S H I Cross coupling
Stereospeclfic alkenyl alumlnum-alkenyl haltde cross coupling catalyzed by Pd or NI
IBuzAIH n Bu fH 5% Pd(PhP}2CI 2
n-au+C  CH  = c
H fC "AI(IBu)= Br f Me
H 2 COzMe
n 8u.
C=C Me
H / , .'/C C /
H COzME
1 Neglshl. E J Am Chem Soc 1976 98 6729
2 Kumada. M Pure Appl Chem 19 $ 0 52 66g
3 Neglshl E Acc Chem Res 1982 15 340
4 Neglshl E J Am Chem So<: 1 987 109 23g3
5 Neglshl E Synthesis 1988 1
Methyl (E,E)-2-methyl-2,4.nonadlenoate (3) 1 To dlChlorobls(trphenylphosphlne)
pailadmJm (0 74 g, 1 retool) in THF (20 rnL) were added sequentially neat d,sobutylatumlnlum
hydnde (0 37 mL, 2 mmol) (10 mln at 25°C) (E) 1 hexenyk.sobutylaiane 1 (obtained Imm 1
hexyne (1 64 g, 20 mmol) In hexane (2O mL) and dllsobutylaiurnlnmJm hydnde (3 58 g, 20
mmol)) Methyl (E) 3-bromo 2 methylpropenoate 2 (3 58 g, 2O mmol) was added (25=C) and
the mixture was refluxed Ior 15 rnln After addlt+on ol 3N HCI, extraction wh EI20, drying
(MgSO4) and evaporation ol the solvent distillation afforded 2 2 g ol 3 (61%) bp 78 79°C/1
K U R S A N O V - P A R N E S Ionic Hydrogenation
A non-catalytic hydrogenation of C=C, C=O, C=N bonds and hydrogenolysis of C-OH, C Hal
etc, under the action of an acid and a hydride ion donor
H3 Ph2SIH z 2 H,
H3CC=CH'(CH 2J2"CH3 "rFA  H3CCH (CH2)3 CH3"
1 3 (80%)
(CH=),I CO=H BF 3 EtzO TFA i,. (CH=), I - CO=H
4 6 (90%)
1 Parnes Z N Ookl Akad Nauk SSSR 1966 166 122
2 Parries Z N Tetrahedron 1967 23 2235
3 Kursanov, D N Synthesss 1974 633
4 Kursanov, D N Ionic Hydrogenation and Related React+ons
5 Volpm, M E, Ed Han,oodAcademcPub 1 985
2-Methylhexane (3) 3 TO 1 (7 84 g, 80 mmol) and Ph2SIH 2 2 (16 21 g, 88 mmol) was added
dropwlse tnfluoroacetk: acid (TFA) (91 20 g, 800 retool) After 1 h stirring at 20°C, it was poured
Into water, neutralized w=th NaHCO3 and extracted with EI20 The dned organic layer was
evaporated Distillation afforded 6 4 g o! 3 (80%), bp 90 92"C n) 0 = 1 3851
6-(2-Tetrahydrothlenyl)-valerlc acid (6) 4 To a mixture of 6-(2 thlenyl)-valerlC acid 4
(5 52 g, 30 mmol) and EI3SH 5 (7 19 g, 62 retool) cooled at 0°C was added drOpwlse a solution
o! BF3 Et20 (1 15 g, 8 mmol) in TFA (30 78 g, 270 retool) After 20 rain st|mng at 20°C the
VOlatlies were removed by distillation and the residue recrystalhzed from hexane to g|ve 3 95 g
of 6 (70%). mp 51 51°C

224 Name and Unnamed Reactions
Name and Unnamed Reactions 225
L A O E N B U R G Pyndine Benzylatlon
Cu catalyzed z- and "pbenzylaflon of pyndine.
,.Ph
HCI pyr Ph
1 2 3
1 Ladenburg, A. LlebgsAnn 1883 16 1410
2 Croock, K.E. J. Am. Chem. Soc 1948 70 416
3 Brewster, JH. Org React. 1953 7 135
2 or 4-Benzylpyrfdlne (3).2 Pyndine hydrochlonde 1 (462 g, 4 tool), CuCI 2 (5 g, 37 mmol)
and pyddine (60 mL) were treated with benzyl chionde 2 (126 5 g, 115 mL, 1 mol) and refluxed
12 h. The mixture was distilled until the temperature reached 195oc. The cooled residue was
treated with water (200 mL) and 32*/. HCI (15 mL), stirred unt|l homogeneous and made alkaline
with 25% NH4OH" Extraction with petroleum ether: Phil, washing the extract wth NH4OH and
evaporation o! the solvent afforded 3 as a mixture o! two Isomers, bp 123-125oc and 175-
190°C.
L A P W O R T H ( B E N Z O I N ) Condensation
Condensation of two molecules of aryl aldehydes to an alpha-hydmxy ketone catalysed by CN"
(va cyanohydnns).
HO O
1 2 3 (76%)
KCN O/
O O HO O OH Ph r "O" "NHI
S (93%)
I Lapworth, A. J. Chem. Soc. 1903 83 995
2 Buck, J.S J. Am. Chem. Soc 19 31 53 2351
3 Hensel, A. Angew Chem. 1953 65 491
4 Ide, V.S. Org. React. 19 4 8 4 269
5 Dahn, H. HelvCh;m.Acta. 1954 371 309,1612
p-Dlmethylamlnobenzplperoln (3). 2 A solution of plperonal 1 (6 0 g, 40 retool) and p-
dlmethylaminobenzatdehyde 2 (5 96 g, 40 retool) in EtOH (30 mL) was treated with a saturated
solut,on of KCN (4.0 g, 61 retool) Xl water After 2 h reflux and 3 days at 20 ° the crystalline
product was filtered and recrystallized Irom EtOH to give 9 18 g of 3 (76.'P/.), mp 132°C

226 Name and Unnamed Reactions
Name and Unnamed Reacttons 227
L A W E S S 0 N Thlacarbonylation
Reagents for synthesis of thlaamdes, th|aesters from the corresponding cadoonyl
compounds
o nux s
1 Lawesson, SO,Schelbye, S Bull Soc Chlm Belg. 1978 87 293
2 Lawesson, S O
Tetrahedmn 1979 35 1339
3 Helmgadner, H Heir Chlm Acts 1987 70 1001
4 Hoffmann, R W
Angew Chem. 1980 42 559
5 Monya, T J. MedChem 1988 31 1197
Dihydro-2(3H)-luranthlone (3).2 Butymlactone 1 (0 86 g, 10 mmol) and [2,4-b|s(4-
methoxyphenyl)-l,3-d|thla 2,4-d=phosphetane-2,4-disuife] 2 (2 02 g, 5 mmoi) in PhMe (10
mL) were heated to reflux until no more Stad|ng matenal was detected (TIC or GC) After
coohng, the solvent was stnpped off and the mixture was punfled on sihca gel using CH2CI 2 as
eluent to afford 3, mp 96-97oc
L E B E D E V Methoxymelhylat|on
Methoxymethyl methyl sulfate 3 as an electroph|lў reagent for methoxymethylaton of alkenes
(CHO)zCH= + SO  CHO- CHz- OSOzOCH 3
1 2
3 + CH=  5
CH 2 CH2OCH.
1 Lebedev, MYu Zh Org Khlm 1987 23 960
2 Lebedev, M Yu Zh Org Khtm U$$R (Eng trans) 19 8 9 25 391
3 Kalyan, YuB Izv Akad Nauk $SSRSer Khlm 1985 9 2082
Methoxymethyl methyl sulfate (3). 1 To a st|fred solution of dlmethoxy methane 1 (6 08
g, 80 mmol) =n CH2CI 2 at 60"C was added freshly d|stdled SO3 2 (6 40 g. 80 mmol) to g=ve a
Solution of 3
1-Methoxy-l-(2-methoxyethyl)cyclobutane 5 To the cooled (-20°C) solution of 3 was
added methylenecyclobutane 4 (2 04 g, 30 mmol) m CH2CI 2 and Ihe mlxlure was stirred for 30
mid MeOH (3 2 g. 100 mmol) was added, then at 20°C TEA (1 01 g, 100 retool) was added
The mixture was diluted with Et20 and washed wllh NH4OH Evaporation of the solvent and
dlStdiation gave 2 19 g of 5 (50%), bp 57°C/15 mm n 0 = 1 4348

228 Name and Unnamed Reactions Name and Unnamed Reactions 229
LEHMSTED - TANASESCU AconeSyntheus
Acrid0ne synthesLs from o-nitrobenzaldehyde and aryis.
1 2 3 (s3)
1 Tanasescu, I. Bull. Soc. Chsm. fr 1927 41 528
2 Lehmsted, K. Chem. Bet. 1932 65 834
3 Spalding, D.P. J. Am. Chem. Soc. 1946 68 1596
4 SIIberg, I. Rev. Roum. Chim. 1965 10 1035
3,S-Olchlomacridone (3) 3 A mixture of 2-ndro-4-chlorobenzaldehyde I (18 5 g, 0.1 tool)
chlorobenzene 2 (78 7 g, 0.7 moO, conc. H2SO4 (37 5 mL) and NaNO2 (O 35 g) was
altamatively shaken for 9 h and allowed to stand 15 h, for a total c 6 days At the end of each
two-day pedod a mixture of H2SO4 (10 mL) and NaNO 2 (0.1 g) was added. The mixture was
poured into water (500 mL) and steam distilled until no fudher aldehyde solidified in the
condenser. The residue from the steam distillation was filtered and digested with Phil, leeving
14 g of 3 (53%).
L E H N Cryptand Synthesis
Synthesis of diaza-polyoxa-macroblcyciic compounds (cjands).
O O O
lOO 0
1 o 2 o / 3 O
N'zH4 
1 Lehn, J M
2 Lehn, J.M
3 Lehn, J.M.
4 Echegoyen, L.
5 Lehn, J.M.
J Chem. Soc Chem. Commun. 19 7 2 11 O0
1973 29 1624
Tetrahedron
Angew Chem Int. Ed 1974 13 406, 611
J. Org Chem 1991 56 1524
Angew Chem InL Ed. 1990 29 1304

230 Name and Unnamed Reacnons Name and Unnamed Reacnons 231
Dlamlne (4) 2 To a suspension ol potassluro phtahmlde 2 (260 g, 1 5 mot) in DMF (1000 mL)
was added bmmo ether 1 (217 g, 0 78 tool) After stlrnng 4 h at 100=C the nllxture was poured
into 3 vol of ca and 5% NaOH The cae was washed (water Me2CO) Recrystallzzatlon (EtOH)
gave 204 g of 3 (85%), mp 104 5-105°C
3 (200 g, 0 65 mol) in EtOH (500 mL) was refluxed with hydrazine hydrate (50 mL) for 10 h,
treated with 6N HCI to pH=l, heated to reflux for 30 min, cooled, filtered and the preclpdate was
washed with EtOH The filtrate and washlrigs were concentrated The SOlid was dissolved in
water, treated with solid KOH and extracted continuously fir a few days with Phil to give 67 2 g
of 4 (70%), bp 115°C (0 2 ram)
Macrocycllc dlamlne (8). 4 (148 g, 68 mrnol) in Phil (500 mL) and 6 (10 8 g 50 mmol, from
oxalyl chloride reaction of the dlacK:l), in Phil (500 mL) were added dropwse simultaneously
stlmng to Phil (1200 mL) over 8 h Evaporation of the solvent and chromatography on alun'na
(Phil and Phil CHCI3 95.5) gave 15 2 g of a diarnlde 7 (75%) To a suspension of LAH (7 6 g
0 2 mol) In THF (120 mL) was added dropwse 7 (13 8 g, 47 mmol) vza a Soxhlet Work up
afforded 8 02 g of 8 75%, mp 115 116°C
Trfiycllc dlamlde (9). From dlamide 8 (5 24 g 20 mmol), acyf chionde $ (4 4 g 20 mmol)
and TEA (4 5 g) using high ddution as for 7 Over 11 h, was isolated 3 67 g of 9 (45%), mp 114
115°C (Phil petroleum Ether)
[2,2,2]-Cryptand (10) Cooled 9 (10 g, 26 mmol) in THF (100 re, L) was treated wflh 1 5 M
dCx)rane (100 mL), the medure was heated to 25"C over 30 min and refluxed for 2 h The
solvent was removed in vacuuro, the crude arolne borane complex was refluxed wlth 6 N HCI
(100 mL) for3 h and evaporated Io dryness The residue was dissolved In a rrunlmuro of water
and passed through Dowex 1 (50 100 mesh as HO ) Concentration to dryness ol the alkaline
and neutral eluent and azeotroplc eilrnlnation of water gave 9 28 g of 10 (95%), mp 68 69°C
(hexane)
L E U C K A R T Thiophenot Synthesis
Formation of thidphenols froro dlazonlum salts and xanthates
C:XCH 3 COOCH
NH 2 NIIN
1 Leuckad, R J Prakt Chem 1890 41187(2)
2 Bourgeolse, E Rec tray Chlrn 1899 18 447
3 TarbeI, DS JAmChernSoc 1952 74 48
3,S-Oichlorothlosaltcyltc actd (3) 3 Methyl 3 5 dchloro 2 amlnobenzoate 1 (43 9 g 0 2 mol)
in 32*/. HCI (50 mL) was dlaZOtlZed with NaNO2 (17 1 g, 0 25 mol) and stirred for 1 h at 5°C Water
(30 mL) was added the solution was neutralized wh NaHCO3 (350 g) at 0°C and back tltrated with
HCI to congo red The cold solution was added to stirred potassium ethyl xanthate 2 (64 1 g, 0 5
rnol) in water (85 mL) at 40-45°C The mixture was stln'ed for 30 rain, extracted with Et20 and the
solvent removed The residue was refluxed for 8 h with KOH (46 6 g, 0 83 mol) in EtOH (150 roL)
The EtOH was evaporated, the solution washed with Et20, the aqueous solution was ac,:hfled, the
product collected and refluxed for 24 h with Zn/AcOH and finally recrystallized from EtOH to afford
31 g of 3 (70%), mp 207 208°C

232 Name and Unnamed Reactions Name and Unnamed Reactions
L E U C K A R O T - p I C T E T . H U B E R T Phenanthndine synthesis
Anlldation of aryls by isocyanates (Leuckardt) or by rn=d (Pict t Hubert, cat-'-ed L _
acids and leading to phenanthddines, a es e - h fz oy Lewis
NCO 
1 2 (73%)
3 4
1 Leuckarol, R. Chem. Bet. 1885 18 873
2 Buttler, JM J. ArrChem. Soc 1949 71 2578
3 Schmutz, I Helv. Chm. Acfa. 1965 48 336
4 Plctet, A,HuberI, A. Chem. Ber 1896 29 1182
5 Boyer, J H Synthesis 1978 205
6 Eisch, J ChemRev 1957 57 525
Hydroxyphenanthrldlne (2) To a suspension of AICi 3 (37 g, 0 25 mol) m o-
dichiombenzene (190 mL) was added o-blphenyl isocyanate 1 (48 8 g, 0 20 tool) over 15 mln at
-?°C. Stlmng was continued for 1 h at 25°C The cnJde product was filtered, washed wdh
u and dned to give 38 g Of 2 (77%), whk:h after recstallizatlon from HOAc yielded 35 6 g
pure 2 (72 6%), mp 292 5-293-5oc. of
LEUCKART . WALLACH ReductlveAmination
Reductlve amlnation of cad:x)nyl groups with amines and formic add or H2-NI (Mk:lUOnac) or
NaBH4 (see Botch).
1 HCO r  2
1 Leuckart, R. Chem. Bet. 1 889 18 2341
2 Waladl, O. LiebigsAnn. 1892272 100
3 Marcus, E. J. Org. Chem. 1960 25 199
4 Moore, M.I. Org. React. 1949 5 301
5 Miquonac, G. C R. 19 21 172 223
6 Raudvere, F. Ann. farm. blo (Buenos Ar) 19 4 3 18 81
N-(1-Pyrenylmethyl)morphollne (2). 3 Moq:)hoiine (65 5 g, 0.75 mol) and 90°/° HCOOH
(38 5 g, 0 75 mol) were heated slowly to 200°C (to dlstitl water, unchanged amine and acid).
To 82 g of the resKue were added 1-pyrenecad:x)xaldehyde I (23.0 g, 0 I mol) and 90%
HCOOH (5 mL). Alter 4 h reflux (182-185=(3), N-formylmoq:oltne was vacuum dlslgled. The
residue was dissolved in Et20 , filtered and dry HCI was bubbled through to give 32.3 g Of 2
.HCI (95%), mp 256-263°C, 2, mp 90=93°C.
BellZylamlna (4).6 NH3 (51 0 g, 3 mol), EtOH (300 mL), 3 (318 g, 3 mol) and Ranay nickel
10 g) were hydrogenated at 90 atm and 40°C. Fiftraton and distdlatlon gave 287 g of 4 (89%),
 70-80°C/8 ram.

234 Name and Unnamed Reactions
L E Y . G R I F F I T H Oxidation reagent
Oxidation of alcohols to cal'oonyl compounds wth a perruthenate catalyst and N-
methylmorpholine. N-oxide (NMO), in the presence of other functional groups
Pr,N Ru04 (TPAP)
OTBOPS OTBOPS
1 2 (7o%)
,Br NMO
TPAP
HO O
1 Ley, S.V.,Griffith, WP. J. Chem. Soc, Chem. Commun. 1987 1625
2 Ley, S.V, Griffith, W.P. Tetrahedron Left.
1989 30 3204
3 Lsy, S.V. AldrichimlcaActa 1990 23 13
Oxlrane aldehyde (2).1 Alcohol 1 (TBDPS ,. tert butyldlphenylstlyl) (0.5 mmol) in CH2Cl 2
(5 rnl.) containing 4 molecular sieves and 4-rnethylmorphollne.N-oxide (NMO) (0 1 g, 0.75
mmol) was stirred ior 10 nan. Tetra-n-propylammonium pemJthenate (TPAP) (8.3 rag, 0.025
mmol) was added and the reaction followed by TLC until complete The mixlure was diluted
with CH2CI2, washed with Na2SO3 solution (10 mL), brine (10 mL) and with saturated CuSO4
solution (10 mL). The organic layer was filtered and worked up to gve 2 (70=/=).
L I E B E N Hypohalide Omdatlon
Oxidation of methyt ketones with hypochlodde (or hypobromlde) to cal'ooxylic adds and
chloroform; with NaOH and ione iodoform Is formed
1 Lieben, A Ltebgs Ann. Suppl 1 870 7 218
2 Fieser, L.F. J Am. Chem. Soc. 1936 58 1055
3 Fusson, R.C Chem. Rev 1934 15 275
2-Naphtholc actd (2). 2 To Ca(OCI)2 65% (250 g) in water (1000 mL) was added K2CO 3
(175 g, 1.27 tool) and KOH (5O g, 0 9 mol) in water (500 mL) with stiffing at 55"C. To this was
added 1 (65 g, 0 5 mot) at 60-70"C by cooling Alter 1 h the oxidant was destroyed by Na2S (50
g in water 200 mL) to give 2, B5 g, mp 181-183°C, from EtOH, 75 g of 2 (87/.), nip 1B4-185"C.
L I E B I G Benzylic Acid Rearrangement
Benzyc acids by rearrangement of diketones (also a-ketol rearrangement)
100 EZ;,O O: , h () )." I 2 (2S%)
" ўOOH
1 Lisbg, v J
2 Warren, K.S
3 Houber, G.
4 Eastham, J F
LJebgs Ann. 1838 25 27
J Org. Chem. 1963 28 2152
Angew Chem 1951 63 501
C)uart Rev Chem Soc 1960 14 221

236 Name and Unnamed Reacnon Name and Unnamed Reactmn 237
L 0 S S E N Rearrangement
Rearrangement of O-acyl hydroxarnio acid derivatives with base or heat to amines or urea derivatlv
(via Isocyanates) or rearrangement of ўarboxylio acids via the.r hydmxamtc aods to arr, nes
Ph--,CN-O-CPh H:zN--C ,oH
o K    .c.o  P--H,C,-H---C,H=(.)
O
1 2 311
COOH . "N'CH "''" 
1 Lossen, W LlebjAnn Chem 1869 150 314
2 Brend. DC J On3 Chem 1966 31 976
3 Popp, FV Chem. Rev 1958 5,8 374
4 Cohen LA Angew Chem 1961 73 260
5 Snyder, HR JAmerChemSoc 1953 75 2014
6 UlrlCh, H J 0n3 Chem 1976 43 1544
N-n-ButyI-N'-phenyl urea (3).2 A solution of potassium O benzoylbenzhydroxamate 1 (0 73
g, 2 6 mmol) and bul/lam|ne 2 (3 0 g. 41 1 retool) in DMSO (30 mL) was Stilted at 30°C The residue
obtained alter evaporation of the solvent was extracted with hot Phil to afford 0 435 g of 3 (83%)
mp 125-128+C (from Phil)
M A C O 0 N A L O Porphynne Synthesis
Porphynne syntheszs from dyrmlemethanes
"H H I 2
+
c.o ," ".
CO,H3 CO=CI-
1
HI HOAc
1 MacDonaid, S P J Am Chem Soc
2 Clesy, P S Austr J Chem
3 Chang. C K J On3 Chem
H.jCCH3
CO=CH= CO=CH.j
3 (11%)
1 960 82 4384
1 965 18 1835
1981 46 4610
5,8-Olmethyl-6,7-bls[2-(methoxycarbonyl)ethyl]porfine (3) 3 [5 5 Olformyl 4,4-d'rmethyl-
3 3 t:,s[2 (methoxycarbonyl)ethyl] 2 2 -d|pyrrylmethane 1 (420 rag), 1 mmol) and 2.2
dipyrrylmethane 2 (150 mg, 1 mmol) dissolved separately in AcOH (150 mL) were mixed
and diluted wth AcOH (200 mL) containing 56% HI (3 5 mL) The reaction proceeded in
the dad( for 1 h Anhydrous NaOAc (10 g) was added and the mixture was aerated for 3O h
in the dark and the solvent evaporated The residue was relluxed wth MeOH (300 mL),
ethyl orthoformate (20 mL) and H2SO4 (3 mL) Alter evaporation ol the solvent and work
up the product was chmmatographed (silica gel, CH2Cl2) The red Iraction was collected
and recn/Stalhzed Imm CH2C12 MeOH to give 15 rng of 3 (10 8%) mp 205°C

238 Name and Unnamed Reactions Name and Unnamed Reactmns 239
M A 0 E L U H G Indole Synthess
Indole synthesis by' cychzation of N-acyl-o-toluidznes.
Cl Me Ct
H
1 2 (94%)
1 Madelung, W. Chem. Ber 1912 45 1128
2 Plchat, L. Bull. Soc. Chlni Ft. 195 4 85
3 Herlz, W. J On3. Cheni. 1960 25 2242
4 Houlihan, WJ J Org. Cheni 1981 46 4511
5-Chloro-2-phenyllndole (2).3 A stwred solutiOn of N-(4-chloro-2-methylphenyl).
benzamide 1 (12 25 g, 50 mmol) zn THF (100 niL) was mamta,ned under N 2 at 0"C and
treated with n-butyllithluni in hexane (0.1-0 15 tool). The StilTed mixture was kept at room
temperature for 15 h, treated wth 2N HCl (60 niL) under ice cooling and extracted wllh
Phil. The combined orgamc layers were concenlrated to dryness to afford 10 6 g of 2
(94%), mp 195-196oC (froni Et20-PhH).
M A K O S Z A Vicarious nucleopl',ltc substitution
Synthesis of alkyl substituted heterocycles by "vicarious" nucleophilic substitution ol
hydrogen in heteroarenes, ndrodenvattves of hateroarenes.
NaOMe _ CN ,CI-ICI
1 Makosza, M J Org. Chem. 1983 48 3860
2 Makosza, M. J Org. Cheni.
1989 54 5094
3 Makosza, M. Acc. Chem Res. 1987 20 282
4 Makosza, M Russian Chem. Rev. 1 9 8 9 58 747
5 Makosza, M. Synthesls 1 9 91 103
2,2-Olchloromethyl-4.nltropyrldlne (3). 2 A solution of 3-nitropyddine 1 (372 mg, 3
retool) and CHCl, 3 (395 rag, 3 3 mmol) m DMF (2 mL) was added dropwtse to a vigorously
sb'red mixlure of NaOMe (650 rag, 12 mmol) in Itqud ammonia (10 mL) at -70 to-68°C. After 1
mm of Stining, NH4Cl (1 5 g) was added, ammonia was evaporated, water (50 mL) was added
to the residue and usual work up afforded 447 mg of 3 (72"/0)

240 Name ad Unnamed Reacnons Name aad Unnamed Reactwns 241
M A L A P R A O E - L E M I E U X - J O H N S O N Olefln (diol) cleavage
Oxatve cleavage o! 1,2-glycols to two carbonyls (Malapde) or direct oxdatmn of oleflns by
IO4 and OsO4 catalyst (Leneux Johnson)
O NalC O O
1 wk CHO
1 OlVle 2 (lOO%) OMe
N=IO4
3 4
Maleprade, L Bull Soc. Chlm Fr 1828 43 683
Baddlley, J J Chem Soc 1954 3826
Fatiatide, A J Synthesis 1 9 7 4 229, 255
Jackson, E I Org React 1944 2 341
Lemleux, R U Anal Chem
1954 26 920
Lemleux, RU,Johnson, WS J On3 Chem 1956 21 478
Rapoport, H J Am Chem Soc 1958 80 5767
Dlerassl, C J Am Chem Soc 196 2 84 2990
Henbest, N R Chem Commun 1988 1036
Olaldehyde (2).2 Glucoslde I (2 8 g, 10 mmol) in water (750 mL) was treated with NalO4
(214 g, 10 mmol) and kept for a week at 20°C F|itratlon gave 2 9 g of 2 (100%). mp 142C
Undecanal (4) Water (5 mL). dioxane (15 mL), dodecene-1 3 (0 71 g 4 2 mmol) and OsO4
(113 rag, 0 044 mmol) were stirred for 5 rnln Powdered NalO4 (2.06 g 9 6 mmol) was added
Over 30 mm and the slurry stirred for 90 rain The mixture was extracted with Et20 and 4 was
isolated as the 2,4-DNPH, 0 96 g, mp 102 106°C, second crop 014 g, total yield 68%
M A N N I C H - E S C H E N M O S E R Methylenaton reagent
Ammomethylaton of activated methyl or methylene groups by in sltu formed Me2N+-CHR
(Manmch) Me2N+=CH2 X reagent for ўў methylenatlon (Eschenmoser)
Me + CH20 + H2N* MezCI- 
4 h M CH= NMe=
O O
1 2 3 4 (90%)
CH212 ч 1SO" + 9 O
Me3N  Me3 N CH21  Me2 N -CH 2  O
6 IDA, Met
5 7 8 (81%) 10 (61%)
1 Mannch, C 191 2 250 647
Arch Phram
2 House, HO JOrgChem 1964 29 1339
3 Tramontlnl M Synthesis 1973 703
4 Dimnoch, D DeParmaze 1986 91 264
5 Bhcke FF Orcj React 1942 I 303
6 Eschenmoser, A Heir ChmActa 1969 52 1823
7 Eschenmoser, A Anjew Chem Int Ed 1971 10 330
8 Roberts, J L Tetrahedron Lett 1977 1621
Dlmethyl(methylene)ammonlum Iodide (Eschenmoser s salt) (8) 7 5 (20 g, 0 36
mol), CH212 6 (120 g 0 73 tool) and EtOH were kept ctosed in the dark for 100 h at 20°C FIRm
lion, washing and drying for 1 h at 70'C in high vacuum afforded 98 g of 7 (B9%), mp 190°C
dec 7 (40 g, 0 122 tool) =n sulfolane (120 mL) was heated under N 2 to lo0"C and CH31 was
distilled Fiitration, washing (CCI4) and dl/ing to 50°C ill vacuum, gave 18 4 g o! 8 (B1%), mp
240' (dec)
(z-Methylenebutyrolactone (10) 7 |Pr2NH(2 02 g. 20 rumor) m THF (20 mL) at 4°C, and
2 55 M of BULl in hexane (20 mmol) was stirred for 15 mn at 78°C Lactone 9 (1 6 g, 19 mmol)
and 8 (7 4 g, 40 mmol) was added At 20'C solvent was removed in vacuum The residue ,1
MeOH was treated wth Mel and stirred for 24 h Chromatography gave 1 21 g of 10 (61%)

242 Name aad Unnamed Reactions
MARKOVNIKOV Regioselectwdy
Descnphon of selectv*y during adddJon of unsymmetncal reagents to unsymmetrical olefins
H-X adds selectively with H forming a bond to the less substituted olef'm cafoon (Markovnkov)
Now supplanted by the general term regJoselectnnty introduced by A. Hassrmr, denoting
selectiwty in bond making between an unsymmetrical reagent X.Y and an unsymmetrical
substmte (now includes regloselechve (o,m,p)-subdubon and also applied to bond breaking
reachons (reg=oselectve el|mnaon)
(CH.j S '''' H Br 20°
+
1 (CHhS 2"
 + Br N.j pentane
Br
N3
regloselectwe additions
400.
1 Markovnlkov, W UebtgsAnn. 1870 153 256
2 Has.sner, A. J Org. Chem 1969 34 2628
3 Sommer, LS J Am Chem Scc 1948 70 2872
4 Nunget, W.A
J Org Chem 1985 50 5370
5 Kharash, M. JAm. Chem. Scc 1940 62 811
6 Mayo, FR. Chem Rev 1940 27 351
7 Stasey, F M
Org React 1963 13 155
Name ad Unnamed Reactio 243
M A R S C H A L C K Aromatic alkyiaton
Alkylahon ol qunones or amnoqulnones with aldehydes
 0 NH z
NaRS20, I [CH:
CH20. 40,
0 1 2 0 (9O%)
ocH co. c
t Marschalck, C BuflSocChtmFr 1936 3 1545
2 Marschalck, C Bull Soc Chlm Fr 1939 6 655
3 Brockmann, H Chem 8er 1958 91 1920
J Chem Soc 1970 657
4 Havhncova, L
5 Krohn, E Angew Chem Int Ed 1979 18 621
1-Amino-2-methylantraqulnone (2). 4 1-Ammoantraqulnone 1 (1 56 g, 6 8 mmol), was
added to a solution of sodium dithlomte (4 42 g, 25 mmol) and 30% NaOH (9 7 mL) The
mixture was stirred at 40°C for 30 rain, then aqueous 35% formaldehyde (0 55 mL) was added
The mixture was stirred for another 5 Ix at 40°C, air was passed through and the product wa.S
hltered, washed wdh water and dned to give 1 45 g of 2 (90%), mp 200°C (It is advantageous to
cam/out the reaction under N2 )

244 Name aad ]nnamed Reacdo Name and Unnamed Reacton 245
M A R T I N Dehydrating reagent
Sulfurane reagent Ior conversion of trans dols to epoxldes, generally for dehydration of dols to
olefns or cyclk: ethers, and as an oxidizing agent
1 2 3 (93%)
1 Martln, JC. J Am Chem Soc 1971 93 4327
2 Martln, JC. J. Am Chem. Soc 1974 96 4604
3 Martin, JC. J Am Chem. Soc. 1977 99 3511
4 Bartlett, P.D. J Am Chem. Soc. 1980 102 3515
5 Eschenmoser, W Heir Chum Acta 19 8 2 65 353
6 Bumett, DA J Am Chem. Soc. 1984 106 8201
7 Martln, JC. OrganlcSynthesls 1977 57 22
3--Chloro-Sc,6c.epoxycholestane (3).2 3-Chloro-Sc,6-cholestandiol 1 (465 rag,
1 O6 rnmol) was added to a solution of bs o",-b|s(tntluoromethyl)bnzenemethenoiato).
diphenylsulfur 2 (1.2 g, 1.B retool) in Et20 After Stlrdng for 10-20 min at 20 ° the phenyl
di(tnfluoromethyl)carblnol was removed by extraction with 20% KOH, after the Et20 was
replaced by CH2Cl 2 (because of the solubility of the carblnol in Et20) After recovery of the
polar sulfoxlde (silica gel, Et20 pentane 1 8) one obtains 417 mg of 3 (93%), mp 97-97 5°C
(EtOH anh).
M A S C A R E L L I Fluorene Synthesis
Synthesls of fluorenes from 2-amlno-2'-alkylbzphenyls via chazonlum ions
2. urea, 7O"
1 2 (40%)
I Mascarelli, l_ Gazz Chm. ltai 1936 66 843
2 Cohen, T JAm Chem Soc 1964 86 2514
3 Puskas, I. JOrg. Chem. 1968 3 4237
2,3,6,7-Tetramethylfluorene (2),3 A mixture ol 2,4,4',5,5'-pentamethyl-2'-aminodlphen-
y 1 (5 35 g, 20 mmol) and 3% H2SO4 (250 mL) was stirred and warmed to form a fine
suspension of am,le salt The suspension was raptly cooled and was diazotized at -2 o to 0oc
With a solution of NaNO2 (1 7°2 0 g, 30 mmol) in water (12 mL) and the reaction modure was
stirred for an additional 1 h at 0oc The diazonlum salt solution was fllterad and heated with 5 g
of urea at 70-75oc. Extraction wth Et20 and evaporation of the solvent gave 1 80 g of 2 (40%),
mp 171"C.

246 Name and Unnamed Reacnons
Name and Unnamed Reactwns
M A T T O X - K E N O A L L DehydrohetogenetlOn
Dehydrohatogenetlon of Ix helokeones with ,4 dlnltrophenylhydrazlne or LlCl DMF
.
I-N" CH3(NO,
I 2 (e/.)
1 Maox, VR,Keall EC J Am Ce oc 1948 70 882
2 Dless, C J  Chem S 1 953 75 3500
3 Wamf E W J  Chem 1 963 28 887
l-Chotesten-3-one2,4.dlnltrophenylhydrazone (2) 2 To a hot solution of 2
chlorocholestane-3 one 1 (0 5 g 1 5 mmol) in AcOH (20 mL) was added a solubon of 2 4
dlmtrophenylhydrazlne (0 5 g, 1 5 mmol) in AcOH (5 mL) After refluxlng for 3 mln under N2 the
mixture was cooled and the precipitate was collected to afford 0 57 g of 2 (88%) rnp 220
222°C
McCORMACK . KUCHTIN . RAMIREZ PhospholeSynthesls
Formation of phosphofes from butadlenes (McCormack) or of dloxaphospholes from 1,2-
dlketones (Kuchtln-Ramrez)
1 2 (72%)
O:=T "CsHs (EtO)= POS,Me 3 C'sHs'q O
O=C CsH s 4, 20 ° C.sHs,/L'-o 'R (OEt)2
3 S (ss%)
1 McCormack, W B U S Pat 2 663 736 2 663 737
2 Halos, AG J O[g Chem 1986 3O 1213
3 Qum, LD J Org Chem 1981 6 461
4 Kuchtln, V A Do/dad Akad Nauk USSR 19 58 121 466
5 Ramlrez, F J Am Chem Soc 1960 82 2651
6 Mltsuo, S J Org Chem 19 81 46 4030
8,6-(EUlylenedloxyl).l.methyl A3-2,4,5,6,7,7a.hexahydro.1 H-phosphindole-l-oxide (2).3
A hexane solution of 1-vinyl 4 4 ethylencfioxycycohex-l-ene 1 (20 0 g, 0 12 reel) and freshly
dltled CH3PCi 2 (18 3 g, 0 156 reel) and copper steamte (0 4 g) as a polymerization inhibitor,
was allowed to stand at rt for 5 days The adduct was filtered and the filtrate was kept for 22
days to get more cycloaduct The first crop was hydrolyzed by NaHCO3, extracted wth
CHCl3, and after evaporation gave 19 36 g of 2 (72 7%), mp 156-157oc

248 Name and ]nnamed Reaction Name and ]nnamed Reaction 249
McFADYEN - STEVENS EsterReductlon
Reduct;on of esters to aldehyde wa hydrazldes.
L.LJ...L.  .'lc.o
--COOE t r* CO'NH= NH2 N -CONHNHSO2P h
1 2 3 (100%) 4 (20"/,,)
1 McFadyen, J.S., Stevens, T S. J Chem. Soc. 19 3 6 584
2 Nieman, C. JAm. Chem. Soc. 1942 62 1681
3 Martln, C.B. J. Org Cheni. 1974 39 2285
4 Ferguson, LH. Chem Rev. 1946 38 244
5 Mosettig,E Org. ReacL 19 5 4 8 232
Plcollnlc aldehyde (4). 2 Benzenesulfonyl chlonde (6 92 g, 40 mmol) was added with
stilting to a chilled solution of plcolinlc hydrazlde 2 (4 62 g, 33 mmol) in pyndine (35 mL). Alter I
h lhe solvent was removed in vacuum, the residue stirred with water, filtered and the solid
washed with EtOH and Et20 to afford 10 5 g of 3 (100=/,,), mp 202-203oc
A mixture of 3 (25 0 g, 0.18 mol), anhydrous Na2CO3 (24 0 g, 0 226 tool) in glycerol (100 mL)
was heated to 1 68°C and nia:ntalned for 2 rain at this temperature To the cooled mixture, water
(100 mL) was added, the solution was saturated wdh NaNO3, filtered and the filtrate extracted
continuously for 10 h wth Et20. Evaporation of the solvent afforded 1 99 g of 4 (20%)
M C M U R R Y Coupling
Formation ol olefins by coupling or cross coupling of ketones, mediated by low valent
titanium Also coupling ol enol ethers of 1,3..dcarbonyl compounds.
HO
0 + o O
I 2 3 (98"/o)
1 McMurry, JE J Am Chem Soc 1974 96 1708
2 McMum/,JE Acc. Chem. Res 1983 16 405
3 Coe, PL. J Chem Soc. PerkJnl 1986 475
4 Dorrnagen, W,Breltmaler, E Chem Bet 1986 119 1734
5 Brsltmann, E SynthesJs 19 87 96
1.(4.Hydroxyphenyl)-l,2-dlphenyl-l-butene (3). 2 To a stirred suspension of
powdered Zn (9.0 g, 0 138 at) in dry dimethoxyethane (DME) at -10°C under N2, "l'lCI4 (12 9 g,
7 5 mL, 68 mmol) was added wa a synnge. The mixture was retluxed for 2 h. To the cold
suspension was added 1 (4 5 g, 22 mmol) and 2 (3 0 g, 22 mtrw:)l) m dry DME (30 mL). The
mixture was relluxed for 4 h, cooled to 20°C and poured into 10% K2CO3 solution (300 niL).
After Et20 extraction (3x100 niL) and evaporation, the light brown oil crystallized on standing
to afford 6 5 g of 3 (98%). mp 109-111"C Ratio o! E Z - 7 1.

250 Name and Unnamed Reacnons 251
M E E R W E I N AIl(ylatlon reagent
R30+BF4 reagent for O-allo/tatlon of amides
H
0 OH OC2H s
1
2 (76%)
NO EC *B LOC.Is (80%)
1 Meerweln, H
2 Eschenmoser A
3 Fullta A.
4 Ayers, W A
5 Curphey, T J
6 McMinn D G
J Prakt Chem 1937 147 17
Pure Appl Chem 1 96 3 7 297
Chem Pharm Bull (Tokyo) 1965 13 1183
Can J Chem 1967 45 451
J Org Chem 1 966 31 1199
Synthests 19 7 6 824
2.6"Olmethyl-4-ethoxypyrlmldlne (2).6 2 6-Dlmethyl 4 hydroxypynmldme 1 (23 0 g
185 retool) was added in small portions to dl/CH2Cl 2 (100 rnL) containing triethytoxomum
tetrafluomborate (MeenNeln reagent) (38 5 g 203 retool) The mixture was stirred under N 2
overnight and then added to 10% Na2CO 3 (500 mL) The organic layer was separated, washed
with Na2CC3 solution (3x50 mL) dned and solvent evaporated D|stdlation of the resx:lue
afforded 21 4 g of 2 (76%) lop 68oc/2 7 torr
MEERWEIN - PONNDORF - VERLEY Reduction
Reduction of carbonyl groups to alcohols by means of AIOPrO)3 and mopropanol
 Al(OiPr) 3
1 2 (76%)
(So'/.)
1 Meeven H
2 Ponndorf. W
3 Vedey A
4 Snyder C H
5 Ashby. E C
60kano. K
7 Denno, N C
8 Wdds. A L
LJebtgs Ann 192 5 444 221
Angew Chern 1 926 39 138
Bull Soc Chin1 Fr 1925 37 537(4)
J Org Chem 1 970 35 264
J Org Chem 1986 51 3593
Chem Left 1987 181
Chem Rev 1 960 60 7
Org React 1 944 2 178
4-Hydroxy-l.2.3.4-tetrahydrocrysene (2) 4 A mzxlure of 4-keto-1.2 3 4-tetrabydrocrysene 1
(2 75 g. 11 mmol) and alumlnum mopropoxK:le (8 2 g. 40 mmol) m PhMe (25 mL) was refluxed
for 1 h After cooling. IPrH (25 mL) was added and the formed acetone was dlstdled slowly
maintaining the volume constant by addlhon of IPrOH After all acetone was distilled, the
solution was acidified with 10% H2SO 4 The separated toluene solution was evaporated to
gNe 2 1 g of 2 (76%). mp 156-158°C

252 Name and Unnamed Reactions
M E I S E N H E I M E R N-Oxide Rearrangement
Chonnatton of pyrtdlnes via rearrangement of N-oxides.
Cl
1 2 3 (58%) 4 (43%)
1 Melsenheimer, j. Chem.Ber. 1926 59 1848
2 Afbert, A. J. Chem. Soc. 1960 1790
3 Brown. E.V. J. Org. Chem. 1967 32 241
4 Pandler, W.L. J. Org Chem. 19 71 36 1720
2"(ancl'4-)Chloro.-1,5-naphthyrldlne (3) and (4).3 1,5-Naphthyddlne 1 (4 5 g, 34 mmoi)
was treated wth a mixture of AcOH (10 mL) and 40% peracetic acid (5 mL) for 3 h at 70C. From
the mixture of mono and oi N-oxides, the mono N-oxide 2 was obtained by reoTstallization from
methylcycfohexane. 2 (0.77 g, 5 retool) was heated in POCI 3 (30 rnL) and P205 for30 ram. The
product was collected and analyzed by GC (15% SE-30 on Chmmosorb W 240oc He 40 ps to b
a mixture of 3 (56.8%) and 4 (43.2%).
MEISENHEIMER - JANOVSKY Complexes
The adduct formed from a polynltmammatic compound in alkaline solution with RO', HO"
(Melsenhetmer) or wth acetone (Janovsky)
1 Melsenhemer, J
2 Fendler, J.H.
3 Jones, P R.
4 Straw, M J
5 Janovsky, I.V
6 Mlchya Kimura
OCH
O2N MeCK  O2N
NO2 NO=
1 2(81%)
o M  0 0
KOH 
3 4(10%)
Lelbgs Ann. 19 0 2 323 205
J.  Cm. 19 67 82 2507
J.O.Chem. 1986 51 3016
Chem Rev. 1970 70 667
Chem. Ser 1886 19 2155
Chem Pha. Buff 1 968 16 634
2,4-Otnltroanlsole-methoxlde complex (2). 2 To 2,4 dinltroanisole 1 (2 47 g, 12 5
retool) m dioxane (3 mL) was added KOMe (0 84 g, 12 mmol) in MeOH (2.4 mL). The red
c,Tstals were filtered under N 2, washed wdh benzene and anh. Et20 and dried to afford 2 27
g of 2 (61%), mp 130-132oc
Janovsky comptex (4). 7 m-Dlntrobenzene 3 (1 00 g, 6 rnmol) in acetone (10 mL) was
shaken vigorously with KOH pellets for 15 rain The purple mixture was filtered, the KOH
pellets washed with acetone and to the combined solutions was added benzene (20 mL)
The black-violet precpttate was recrystallized Imm benzene-acetone to give 135 rng of 4
(10%), mp 250°C.

2.54 Name and Unnamed Reacnon,ў
MELDRUM S Ac
A cycle malonate denvatwe (aCldў methylene) used in place of maJonate in alkylatlons or
reactions with aldehydes
Mel 4
0
(49%) 5 6 (eO%)
1 MeldnJm, A N J Chem Soc 1908 93 598
2 DavKLon D J Am Chem Soc 1948 70 3426
3 Chau, C C Synthess 1 984 224
4 Dh,mane, K Tetrahedron Lett 1987 28 885
5 P,ng, L Org Prep Proced Int 1 992 24 185
Meldrum's acid (3) 2 To malone acўl I (52 g, 0 5 tool) ,n acetў anhydnde (60 mL. 0 6 tool)
was added conc H2SO 4 while Stlmng Acetone 2 (40 mL, 0 55 tool) was added Coohng for
24 h, filtration, washing the solid with ce water and recrystalhzaton from acetone-water gave 3
(35 g, 49%). mp 94-95oc (dec)
Dimethylmalonic acid (6) To a suspensx)n of s,lver (:ўle (26 g, 0 5 moo m MeCN (50 mL)
end Mel 4 (20 mL, 0 33 tool) was added 3 (14 4 g. 0 1 tool) ,n MeCN (50 mL) over 1 h After
stlmng and 24 h standing, f'dtratlon and evaporation of the solvent, the oily residue was treated
with water Filtration gave dlmethyl MeldnJm acid 5 12 6 g (73%). vacuum dlstllletlon gave
11 8 g, bp 127-129,/33 ram, mp 59 5<'C To a 2M HCI solution was added $ (3 44 g, 24 retool)
and the mlxlure was boded Cooling and filtration afforded 6 2 1 g (80%), mp 192 193°C
(dec)
Name and Unnamed Reacnons
M E N C K E - L A S Z L O Nitration of Phenols
Olho nitration of phenols by metal rtrates Also oxidation ot mercaptans Io dlsuffldes
O O
"Clayfen"
HO Fe(NO3h HO
1 2 (S5"/.)
1 Mencke JB Rec Tray Chum PaysBass 1925 44 141
2 Laszio P Tetrahedron Left 1982 23 5035
3 Laszio P Tetrahedron Lett 1983 24 3101
4 Laszio P J Org Chem 1983 48 4771
5 Laszio P PureAppl Chem 1990 63 2027
2-Nltroestrone (2).4 "Clayfen" was prepared from a mxture of Fe(NO3) 3 H20 (45 g 0 11
tool), K 10 bentonite clay and Me2CO (750 mL) Freshly prepared "Clayfen" (2 0 g) was
added to estmne 1 (0 54 g 2 retool) and PhMe (150 mL) The suspension was stirred
overnight at 20 ° and filtered under vacuum The yellow f,ltrale was purlf,ed by cOlumn
chromatography on sllca gel (n-hexane EIOAc 8 2) Evaporation of the corresponding fraction
afforded 0 347 g of 2 (55%) mp 178 180°C

256 Name and Unnamed Reacnns Name and Unnamed Reactu 2.57
M E N Z E R Benzopyran synthesis
Benzopyranone synthesis from phenols and  keloesters or unsaturated acids
+ 24O 250oc
HO OH O Ph 45 h HO Ph
1 2 3 (33%)
OH O
HO OH HC /
1 Menzer Ch CR 1952232 1488
2 Lacey RN J Chem Soc 1954 859
3 MercJer Ch CR SeneC 1973273 1053
2-Phenyl-4(4H)-one-5,7-dlhydroxy.l.benzopyran (3) 1 A m,xture of phiorogluc,nol
1 (2 77 g 22 mmol) and ethyl benzoyiacetate 2 (7 65 g 40 retool) was heated to 240 250"C for
1 5 h The cooled mixture was extracted with 5% NaOH and the aqueous solution was
extracted with Et20 Acidification afforded a brown product which after subhmatlon at 250
300°C/0 01 mm and recrystalhzatlon from EtOH gave 2 2 g of 3 (33 5%) mp 278°C
M E R R I F I E L O Peptlde synthesis
Growing of a polypeptўle cha,n by attachment of the f,'st arr,radd to an msoluble polymer and
attaching successively ammoaclds At the end cleavage of the peptide from the polymer
Cbz L vahne 3
Polystyrene CH(NO2)-CH2CI TEA  [-'H,O-C-CH NH.Cbz
2 "-' [11 4
O iPr
HBr I-=-L'- A ^ ^' "NH2 Cbz-lyclne $
HOAc 50 I Pr DCC
._CH.NH..CHz.NH.Ct) z 1 HBr HOAc
- II I II 2. NaCH II I
O iPr O O IPr O
7 8
1 Merrlfleld RB JAm Chem Soc 1983 85 2149
2 Memfield RB J Org Chem 1964 29 3100
3 Dorman, LC J Org Chem 1969 34 156
4 W0nsch, E Angew Chem Int Ed 1971 10 786
L-Valyl polymer (4) 3 (15 5 g 61 7 mmol) TEA (8 65 mL 61 7 retoOl) and EIOAc (350 ml.)
was refiuxed wdh polymer 2 (40 g) for 48 h, AcOH (12 ml.) and TEA (28 mL) was added and
refluxing for 4 h Fdtraton and washing (EIOAc EIOH H20, MeOH) yielded 48 9 g of 4
Polymer (5). 4 (10 g, 5 6 mmol val,ne) and 30% HBr m AcOH (30 ml.) was shaken for 5 h at
25C, diluted with AcOH (50 ml.) filtered washed (AcOH, EtOH, DMF), to afford 5
Pofymer (7) 5 (10 g) was treated w,th Cbz-<jlyc,ne 6 (2 34 g. 11 2 mmol) ,n DMF (20 ml.) N-
ter 20 nln shaking, DCC (2 31 g 11 2 mmol) n DMF (4 6 mL) was added and shaken for 18 h at
25°C After filtration, more 6 (1 17 g) and DCC (1 16 g) was added and al shaken for 2 h Fiitra
ten, shaking wdh AcOH (3 ml.) and TEA (1 ml.) and wasl'ung (DMF,EtOH and AcOH) gave 7
GlycyI-L.vallne (8) 7 was decart)obenzoxyiated with HBr AcOH and shaken with 2N NaOH
(4 5 ml.) in EIOH (40 5 mL) for 1 h at 25°C 8 was punf,ed by x)n-exchange chromatography

258 Name and Unnamed Reactions
M E Y E R S Asymmetnc synthesls
Chral oxazoles in asymmetric synthesis of carboxylic acxCs, aldehydes, choral
dihydronaphthaleoes.
O.kPh
-79"C Ou 2 N "' M H'CBu
 1 2e -7'C "
3 (ee%)
Ph. --OMe
OMe OMe OCH
1 Meyers, A.I. J. Am. Chem. Soc 1974 96 268
2 Meyers, A.I. Acc. Chem. Res 1978 11 375
3 Meyers, A.I. J. Am. Chem. Soc. 1976 98 567
4 Meyers, A.I. J. Org. Chem
1980 45 2785
5 Meyers, A.I. J. Org. Chem.
1987 52 4592
6 Meyers, A.I. J Am. Chem. Soc. 1988 110 4611,7854
7 Meyers, A.I. Tetrahedron 1989 45 6949
(S)'(+)-2-Methylhexanoic acid (3).3 (4S,5S)-1 (15.4 g 70 mmol) in THF (160 mL)
under N 2 at -78"C, was treated with IDA (from 9.8 mL of ,Pr2NH and 2.2 M n-But.J (33 mL)
in THF 75 mL) over 20 rain. After 20 rain tha mixture was cooled Io -98"C and Bul (14.7 g,
80 rnn-x in THF (20 mL) was added over 20 mln. After 2 h at -98"C the mixture was warmed
to 20°C, poured into bnne and exlracted with Et20 Bulb to bulb distillation afforded pure 2
24
{(zJ589 = -32 2" The crude oxazoline 2 (17.2 g) was refiuxed for 3.5 h ,n 4N H2504
Extract,on with Et20 (3.75 mL), wash,ng with 5% K2CO 3 (3x100 mL), acldificatxn (pH=l) of
the aqueous exlract with 12 M HCI and extraction with Et20 ' gave on distillation 5 8 g of 3
24
(66%), [r]SS9 = + 14
Name and Unnamed Reactions
M E Y E R - S C H U S T E R Propargyl alcohot rearrangement
Add catalyzed rearrangement of acetylene alcohots into o..]-unsaturated cattx)nyl derivatives
HzSO
Ph :H.C==CH ---------.--e- Ph-CHoCH.CH.O
115"
OH 1
2 (33%)
1 Meyer, K.H,Schuster, K. Chem. Ber. 1922 55 819
2 McGregor, WS. J. AmChem. Soc. 1948 72 183
3 Swaminathan, $. Chem. Rev. 19 71 71 429
4 Huggllf, H.P.W. J. Chem. Soc 195O 335
Clnnamaldehyde (2).2 Phenyl ethynyl carb,nol 1 (5 4 9.40 retool) and water (5 mL) was
distilled with steam Into 28% H2SO 4 (25 mL) heated at 115°C. The crude ody product 3 1 g
(57%) was separated as the phenylhydrazone by treatment with phenyl hydrazlne
hydroctdde (17 5 g, 0.12 moo and NaOAc (10 g) m water (150 mL) to afford 3 0 g of crude 2
phenylhydrazone (33%), mp 154o157oC Two recrystallizations from EIOH ra,sed the mp to
168-169"C.

260 Name and Unnamed Reactions
Name ad Unnamed Reactions 261
M I C H A E L Addition
Base promoted 1,4-additions of nucleophlles (usually C) to o..-unsaturated esters, kelones,
n,tnles, sulfone nitro-compounds; often stereoseteclive addition.
H
O O
2
C ° °
 MeO OMe
O chlral crown ether
(80%)  oo
O 0 0 Ph 0
(98% Z') t Bu Ph  Ph t Bu
" (87%) g8% anti
Komnenos, A. Liebgs Ann. 1883 218 145
Michael, A. J prakt. Chem 1887 35(2)348
Heathcock, C.H Tetrahedron Lett. 1986 27 6169
Yamaguchi, M. Tetrahedron Lett. 1964 25 5661
Enders, D. Tetrahedron 1966 42 2235
P,ers, E Can. J. Chem 1969 47 137
Seebach, D Helv. Chsm. 1985 68 1592
Bergman, E.D. Org. React 19 59 I0 179
Heathcock, C H. Topes m Stereochem 1 9 91 20 87
Eremophll-ll..en-3-one (3).8 To a slurry of Cul (6.0 g, 31 5 mmol) ,n ether (120 mE) at 0"
(N2) was injected 1 59 M MeLi in ether (39 4 mL, 62 5 mmol). To the resulting 2 was added 1
(2.0 g, 10 mmol) in 80 mL ether over 20 rrdn After 2 h at 0 o the mixture was poured nto 1 2N
HCf (800 mE) and exlracted with ether Evaporation gave 1.9 g of 3, bp 123-124/0.03 ram,
semlcarbazone mp 191.5-193.5 o.
MICHAELIS - BECKER - NYLEN Phosphonylation
Nuc]eophllic attack of hthlum dialkylphosphonates on pyndium selfs to produce pyridine
phosphates
-"--"-" - (OEt
MeSO 4 2 - (OEt):,
" OMe
0
1 3 ($7%)
1 Michaelis, A.,Becker Chem Bet. 1897 30 1003
I Mlchaells, A, Chem Bet. 1898 31 1048
2 Nylen, T Chem. Ber 1924 57 1023
3 Gordon, M J. Org. Chem. 1966 31 333
4 Redmore, D J Org. Chem. 1970 35 4114
S Kemm, KM J. Org. Chem 1961 46 5188
Olethyl pyrldlne-2-phosphonate (3). 4 n-Butyhthlum (23% in hexana) (63 mL, 0.15 toOl)
was added dropwlse to d,ethyl phosphonate (25 0 g, 0 18 moo at -20 to -30°C over 2 h. To the
resulting 2 was added N-methoxywnd,nlum methosulfonate 1 (from pyddlne N-oxide 14 3 g,
015 tool and dlmethyl sulfate 18 9 g, 015 mol) in diethyl phosphonate (40 mL) over 1 h at
-15C The rr,xture was stirred at room temperature overnight and water was added (100 mL).
Nter extraction with CHCI3 (3x75 mL), the organic layer was extracted with 4N HCI, baslfied and
reextracted to yleid 22 9 g of 3 (67%), bp 105-112°C (0.08 mm). Redistilfabon gave pure 3, bp
96-97"C (0 03 ram), pcrate mp 86-87°C

262 Name and Unnamed Reactior Name and Unnamed Reactions
M I E S C H E R Degradation
Three cadx)n degradation of a caoxylic acid side chain (see Bad:)ier-Wleland).
R
HO"
1 Miascher, K. Heir Chlm.Acta. 1944 27 1815
2 Spdng, F.S. J. Chem. Soc. 1 9 5 0 3355
3 WeCsteln, A. F.xper/enba 1 9 5 4 407
3 r'Oxy-12--acetoxypregnall.20.one (4).1 To diphenylcholene 2 (100 g, 0.14 rnol)
in boiling CCI 4 (500 mL) was added NBS (40 g, 0.23 tool). After 10 rain reflux the mSdum was
filtered, the filtrate treated with dlmethy(arllline ($00 g, 0.23 moO, the CCI 4 disBed, the
residue diluted with ether and extracted with dil HCI. The residue after evaporation of the
solvent (100 g) was c'stalitzed from acetone-water. Reacetylation (Ac2)/py) gave diene 3 (28
g). To  pn:Kuct in AcOH (100 mL) was added CrO3 (20 g, 0.2 tool) m water (20 mL) and
AcOH (100 mL) dropwtse over 1 hr at OoC. After 15 h sifrdng at 20oc, Me(:-I (50 mL) was
added and the solvent removed in vacuum. The residue was treated wh aq NaOH and
filtered to obtain crude 4 (24 5 g) punfied with Girard reagent.
M I L A S Oiefln Hydroxylation
Hydroxylabon of a double bond to a 1,2-dtol with hydrogen peroxide and OsO4 as catalyst.
2 a (23"/.)
2 b (,l,JSp) (28"/.)
I Mdas, W.A. J. Am. Chem. Soc. 1936 58 1302
2 MIlas, WA. JAm Chem. Soc. 1959 81 3114
4r,-Sr,-Dlhydroxycholestan-3-one (2a) and 4-5-dihydroxycoprostan-3.one
(2b). 2 To a solution of cholestenone 1 (4 g, 10 retool) in ethyl ether 050 mL) was added a
solution of OsO4 (0.2 g) in ethyl ether (10 mL) and hydroxgen peroxide 30% (5 mL). After 24
h at 20"C the solvent was removed under vaoJum for 24 h. If the rasidue dadened, a few mL
di hydrogen peroxide were added and the operation repeated. The rasKJe was dissolved ,n
hot EtOH (50 rnl.) and cook)d to give 2s, 1 00 g (23%), mp206-208oc. Fom the filtrate by
dilution with water separated 2b, 1 20 g (28%), mp 112-112.5"C, after rec/staifizaUon from
ethanol.

264 Name and Unnamed Reactwns
Name and Unnamed Reacnon,ў
M I L L E R - $ N Y D E R Atyl Cyanide Synthesis
Synthesis of benzondnles from aldehydes via oxlme ethers Formab, on of P-cyanophenol from
ndrobenzaldOx,me and P-ntrobenzontnle (used as a SOmebrnes recyclabte che,n carder)
1 NO l 3 (83%)
HC--O C=N
1 MIIler, MJ,Loudon, GM J Org Chem 1975 40 126
2 Snyder M R J Org Chem 1 974 39 3343
3 Snyder, M R
J Org Chem lg75 40 2879
p'Cyanophenol (3) 3 To a heated (70oc) mzxture of anh Na2CO 3 (4 24 g 40 retool) n DM$O
(25 mL) was added a solubon of P-ndrobenzaldox,me 1 (3 32 g, 20 retool) and p-n,trobenzondrile
2 (0 15 g, 1 retool) in DMSO (35 mL) The orange mixture was heated to 114°C for 10 h and was
poured into ce water (150 mL) contalnln 32% HCI (5 mL) Extraction with Et20 and reextracton
from Et20 with 5% NaOH followed by acidification and recstalhzation afforded 1 97 g of 3 (83%),
mp 103-107"C, recrystallized from phil, nip 111 112oc
MfNISCl Aromatic aminaton
catalyzed free radial ammatton of aromatics or free radical carbamylatlon of protonated
heterocycles
Me/1 2 3 (76%)
 H202 CONH
4 5 6 (82"/.)
1 Minlsc, F
2 Mlnlscz, F
3 Mlnlscl, F
4 Minlsc, F
5 Heinisch, G
6 Mlniscl, F
Teahedron Lett 19 6 6 433
Chem Ind (MIlano) 1966 48 716
Teahedron Left 1 9 7 0 15
Synthesis 1 9 7 3 1
S ynthes ss 1 9 8 6 119
Tetrahedron 1986 41 4157
N,N Dlmethylanlllne (3) 2 To N-chlorodlmethylarrdne 1 (4 3 g, 0 054 tool) HOAc (50 ml.),
Phil (30 mL) and H2SO 4 (83 ml.) was added wth stlrnng fnely powdered FeSO4 The
temperature rose from 15°C to 27"C wthln 5 m,n After 15 min the mixture was poured into ice
made basic (NaOH) and exlracted wth Phil Distillation gave 5 0 g of 3 (76%), bp 193-194°C
Qulnoxallne 2-ўarboxamlde (6) 3 Qu,noxa,ne 4 (13 0 g 0 1 tool) and 98% H2SO 4 (5 5
mL) in 5 (100 mL) was treated smuitareously with 34% H202 (15 0 mL, 0 15 mol) and FeSO4
7H20 (41 7 g, 0 15 mol) with efficient st,rdng at 10 15°C for 15 rain Excess 5 was distilled and
the residue extracted with CHCI 3 Evaporation afforded 14 2 g o| 6 (82%), mp 200°C

266
Name and Unnamed Reaction
rs s , - slgrnevoplc rearrangement of  sulfoxkJss o a su
cleaved by PhOsphitas to alfyc alcohols, t  lenatas which are
I Misiow, K.
J-Am.C,ern. Soc. 1966 88 3138
2 Braverman, S. Chem. Commun.
3 Evans, D.A. 1967 27O
4 Evans, D.A. 1971 9,3 4956
Acc. C,em. Res.
1974 7 147
5 Grieco, P.A. J. Chem.  Chem. Commun. 1 972 702
6 Gneco, P.A. J. Org. Chem.
1973 38 2245
(+)'{E)-NUClferole (3).S To 1 ($95 rag, 1 retool) in THF (10 mL) at -50"C under N2, was
added dropse 1. M eul.i in hexane (0.65 mL, 1.08 retool). 2 (5,18 rag, 15 mmof) in THF (1
mL) was added dre °Ver 10 m/n. The mlxlura was stirred at .50oc for 1 h and at 25oC for
2 h, POured Into brine and extracted with Et20/hexane (3:1). After distillation the residue
wasdissolved in MeOH (1.5 mL) and added to benzenelho| (660 rag, 5,4 mmo) 1 MeOH (20
mL). 1.66 M BuU (0.78 mL) was added  N2 ' and all was heated fr 7 h at 65°C, then
kept for 10 h a 25oc. Quenching with water, extraction (Et20) '
by preparative TLC (s,licaget evaporation and purification
Et20/hexane 2:1) afforded 127 mg of 3 (58%).
Name and Unnamed Reaction
M I T S U N 0 B U Displacement
Inter and Intramolecular nucleophdic displacement of alcohols with inversion by means of dtefl
azodicartxylate (DEAD)-triphenyhosphne and a nucfeophds. AJso dehydration,
ssterfflcatk)n of alcohols or alkylaflon of phenols,
]OH O° CO4e
PhP ,
: DEAD •
1 )H HO'"
O ч HO O
Ph 2 (77%)
OEAO, 2O °
1 Mitsunobu. O. Bull Chem. Soc ,[pn. 1967 40 2380
2 Miller. M,J. JAm Chem. Soc. 1980 102 7026
3 Evans, S.A. J. Org. Chem.
1988 53 2300
4 McGovan, D.A. J. Org. Chem.
1981 46 2381
5 Mitsunobu. O Synthesis
1981 1
6 Crich, D. J. Org Chem. 1988 54 257
7 Hassner, A. J. Org Chem.
1990 55 2243
(')Methyl ўla'3"hydr°xy'4,5"oxycyctohex.l.enecarboxylate (2). 4 To (-)methyl
sate I (220 rag, 1.06 mmo) and tnphenyfphosphne (557 rag, 2.12 mmo0 in THF at
under N2 was added with stlmng (DEAD) (370 rag, 2.12 rnmol). After 30 mm at
20°' it was vaCUUm dlst,lled (Kugelrohr) at 165oc (0.1 ram) and taken up in Et20" Cooling gave
bls(ca,'bethoxy)hydrazine (10 mg mp 133oc). The filtrate was concentrated and
Chromatographed (preparatk, e TLc-sdtca gel Et20) to afford 140 mg of 2 (77%) on Standing;
recqfstallized from Et20.petroleu m ether, mp 81-820C, (z)5 ,.. 55.4 o.

268 Name and Unnamed Reacttons
M U K A I Y A M A Stereoselectve aldol
Stereoselectwe aldol condensation v,a tm (11) enolates (e g 2)
o OSnOYf
 ,ssoo-..__.__.__._, ...Ls ' h c"
1
2 3
o
Ph + Ph
_-
$E!
4 (syn)
1 Uukayama T Chem Lett 19 82 353
2 Mukayama T J Am Chem Soc 1 9 73 95 967
3 Mukayama T Chem Lett
1986 187
4 Mukayama T Org React
1962 28 187
Syn 3"(Ethylthfomethyl)-4-hydroxy.6.phenyl.2.heXenone (4) and anti (5)3 To
ethanethlot (10 0 mg 0 17 mmol) in THF (2 mL) was added 1 64 M n butyltlthlum in hexane
(0 11 mL) at 0°C under Ar Stannous It*flare (69 0 mg 017 retoOl) was added and after 20 rain
the rr)lxture was COOled to 45oc Methyl vinyl ketone 1 (1 t8 mg 1 98 mmol) in THF (1 5 rnL)
was added followed by 3 phenylpropanal 3 (350 mg 2 61 mmol) in THF (1 5 mL) After 12 h
aq ctnc acid was added and the organў material extracted with CH2CI 2 The residue after
evaporation was dissolved in MeOH and treated with Cltnc acўl After 30 rnm stlmng, the mixture
was quenched with pH 7 phosphate buffer extracted with CH2CI2 ' the solvent evaporated and
the residue chromatographed to afford 336 mg of 4 (75%), syn anti (90 10)
Name and Unnamed Reacnons
M U R A H A S H I Nlybc Alkylatlon
Nlyllc alkylaton of allyt alcohols in the presence of copper Iodide and phosph,n,mmes
CuN Me
3 (70%)
H
• ,c.. r. ,./=C..... (eo 8o%)
1 Murahash,,SI JAm Chem Soc 1977 gg 2361
2 Lovlsalles, J J Organomet Chem 1977 136 103
3 Murahash,,SI JAm Chem Soc 1978 100 4610
4 Tmst, BM J Org Chem 1980 45 4256
5 Goedng, NL J Org Chem 1961 46 2144
6 Fan C, Cazes, B Tetrahedron Lett
1966 29 1701
(Methylphenylamlno)trl-n.butylphosphonlum Iodide (2). 5 Phenyl azlde and Bu3 P in
Et20 afforded the Phosphmlmme which with excess of Mel gave 2, (from EtOAc)
3,&'Dlmethyfcyclohexene (3). C,s 5 methyl 2-cyciohexencl 1 (1 12 g, 10 mmol) was
treated with MeU (in Et20)(6 7 mL 1 4 M) and all was added to a suspension of Cul (1 90 g,10
mmol) in THF (20 mL) After 30 mm the homogeneous solution was chdled to 78"C and 1 49 M
solution MeU (6 7 mL) in Et20 was added followed by 2 (4 35 g, 10 retool) in THF (40 mL) After
3 h strring at 20 °, the medure was quenched by sat NH4cI (30 mL) The Et;,O layer was washed
and evaporated to grve 763 mg of 3 (70%) purified on a GC-capdlary column

270 Name and Unnamed Reacnon.s Name and Unnamed Reacnons
N A Z A R O V Cyclopentenone synlhesls
Acid catalyzed cycllzaton of dlenones to cycopentenones
O O
1 2 (3o'/.)
O
Me StM te H
4 (78"/.) (22%)
1 Nazarov, J N Bull acad so (USSR) 19 46 633
2 Manno, Jp J Org Chem 1961 46 3696
3 Denmark. SE Tetrahedron 1986 ,/2 282t
4 Peel, ML TetrahedronLett 19B6 27 5947
2"(Carbethoxy)-3-methyl-3,4,5,6-tetrahydro.2H.pentalen.l.one (2).2 A solution
of ethyl 2.ethytidene-3-(1-cyclopenten. 1-yl)-3-oxo-propanoate 1 (210 mg, 1 mmol) in CH2CI 2
(10 rnL) was stirred with SrlCI4 (780 rag. 3 mmol) for 24 h at 20°C After quench,ng with water
(50 mL), the orgamc tayer was washed (NaHCC)3) ' dried (MgSO4) and puted by preparative
TLC to afford 62 5 mg of 2 (3)
N E B E R Rearrangement
Rearrangement of N.N-dirnethylhydrazone or tosylate derivatives of oxime to azldnes and
from there to (z-amino ketones.
HCI S NHz
NH-I-CH,--I-NH, NH--I
CI" v "CI NH z
3
1 Neber, P W IelgsAnn 1926449 109
2 Neber, PW IelgsAnn 19311526 277
3 Morow, D H J Org Chem 19 6 5 30 579
4 Hyalt, JA J Org Chem 1981 46 3953
50'Bdne, C Chem Ray 1964 64 81
6 Yamma, Y Synthests 19 7 3 215
171}'Amln°'31}'hydroxy'17c{-prag-5-en-20-one (2). 2 To 2'-(3l}-hydroxypregn-5-en-
20-yllde)-I ',1 ',l'-tnmelhyl hydrazomum Iodcle I (15 0 g, 38 6 n11ol) in DMSO (100 mL) and
anh. EIOH (1000 tnl.) was added 51% Nail m mineral oil (7 5 g) After 2 h reflux the mixture
was concentrated in vacuum to 150 tnL and poured into water (1000 mL) Extraction with
Phil Et20 (1 1), washing the extract and evaporation gave an oil which was heated with 6N
HQ (10 mL) and F.JOH (250 mL} for30 mm at 95°C The mure was I:XUrad into water (1000
mL) and filtered to gwa 5 4 g of 2 (42%)

272 Name and Unnamed Reactions
Name and Unnamed Reactions
N E B E R - B O S $ E T Ox,ndole-cmcoline synthes,s
Synthes,s of N-ammooxindols or of onnolines.
 .... CHzCOzHpd/c ' CHzCOzH1. N a., 2N  ------CHCO2H O
z v -NH z 2. SnCl 2 v -NHNH 
OH 3 4 (50%) tNH2
v -NH z  v -NHNH z  
1 Neber, P.W. LseblgsAnn. 1929 471 113
2 Bosset. G. C.Z. (Ph.D. Thews) 1920 fl 3015
3 Baumgarten, H F. J. Am. Chem Soc.
1960 82 3977
1-Arnlnooxlndole (4).3 A solution of o-nltrophenylacetlC acid 1 (20 g. 0.11 tool) as the Na salt
was hydrogenated in the presence of 10% Pd on C (0 5 g) After removing the catalyst by
fillration through Cede, the Ooamlncphenytacetic acid 2 was diazotized with NaNO2 (7 7 g0 0 11
mot) and after cooling conc. HCI (84 mL) was added. The dlazonlum sail of 2 was treated wdh
SnCI2 2H20 (75 g, 0 33 mol) in HCI (75 mL). The mixture was stirred for 30 rain and
maintained for 24 h at 0°C. Treatment of Iin sail with H2S ' removal of the Sn$, concentration of
the filtrate and subllmation of the residue in vacuum afforded 7 48-8 46 g of 4 (46-52%), mp
125-126 5C.
N E F React;on
Conversion of nltroalkanes to carbonyl compounds by acidification of nitronates.
 1. NaOH 0
2. 2NHCI ,
NO2
1 2
1 Nef. J.U. LseblgsAnn 1894 28O 263
2 Wemstein, B. J Org Chem 1 9 62 27 4049
3 Langrene, M CR(C) 1974 284 153(3)
4 Noland. WE Chem Rev 1955 55 137
5 Miyakoshy, T Synthesis 1986 766
6 McMurry0J Acc Chem. Res 1974 7 281
7 Plnnmk. H W Org. React 1 9 9 0 38 655
1,2,3,4,5,6,7,8,9.10,11,12-Dodecahydro-S.ketophenentrena (3).2 A cold solution of NaOH
(5 g, 0.125 moo in EtOH (100 mL) was added slowly to • ch.lled st.rred solut of
1,2.3,4,5,6,7,8,9.10.11,12-dodecahydro-9-nltrophenantrene 1 (10 9 g, 0 0424 mo O in EtOH
(100 mL). The mixture was maintained at 0-2°C under N 2 for 3O rln and then poured into
cold 2N HCI (3OO mL) The solution was stirred for 2 h at 5°C and allowed to warm to 200C
over a day. The organў matena! was exlmcted with Et20 (3x300 mL), the extract dned and
the solvent removed to give • brown resclue 9.5 g (mixture of 2 end 3) Heating isomensed 2
to 3 Dstlllat;on of 1 g crude product gave 0 46 g of 3 (46%). bp 70°C/0 12 mm; DNPH. mp
231-231 5°C (EtOH)

274
Name  Unzmed Reacno,t
N E N I T Z E S C U Indole Synthesis
Indole synthesis from quinones and amino crotonates
- JL .... o
 NH  It )l I
I o 2 2 .......oHN H 2
3
MeOOl EI OH
CH CH
H
4 (%) OH O 5 (23%)
1 Nenltze, C D
Chem Ber 19 2 5 58 1063
2 Nenle. C D Bug  Chlm .,ore
3 Allen. GR 1929 11 37
J O Chem
1968 33 198
4 Bemўl. JL J O Chem 1981 46 4197
5 Rerey. T s J Chem 1984 37 1263
6 Allen, G R Jr O Ream 1 9 73 20 337
Ethyl 4"Carb°meth°xy'5"hydroxy-2-methyllndole.3.carboxylat e
5'8"dlhydr°xy'methyllsocaostyrll.4.carboxylate (4} and ethyl
(5) 3 1 (850  5 retool) a 2
(5 mg 5 1) In EtOH (10 mL) were reflux for 2 h Aer reval of the sONent, the rese
was tur with Et20 a fier to gNe 871  Of 3 (59%).  132 5-1 5C 3 (1 96 g.
6    2 (200 , 1 2  in AH (30 mL) w heal on a eam bath for 15 h 
eVrat e rescue s sso in ErOs. Ire wdh Cal. fler and arat
e reSCue was t wh CHI 2 (25 mL} to gNe 3
CH2C flte w chmmgraph on  of 5 (23%).  2 254"C e
(30%),  141 1oC gnes sll a all to o 5  of 4
Name and Unnamed Reactions
N I E M E N T O W S K I Qu|nazolone Synthesis
Qulnazolone synthes,s from anthranlllc acid
o
+ H 2 120" N
v -NH 2 o = CH
H
1 2 3 (90%)
1 v Niementowsk, S J Prakt Chem 1895 51564(2)
2 Eddlcott. MM J Am Chem Soc 1946 68 1299
3 Pater. R J Heterocycl Chem 19 71 8 699
O ' D O N N E L L Amino Acid Synthesis
Amino acid synthesis by alkylatlon of glyone denvahves
N. C(C, H0 * p-ON CH, CHa  :N C_ C
NH"
1 2 3 (80%)
10Donnell MJ Tetrahedron Lett 1982 23 4259
20Donnell MJ TetrahedronLett 1984 25 3651
30 Donnell. M J
Synthe$1$ 19 8 4 313
40'Donnell. M J
Chem Comrnun 19 8 5 1168
P-Nltrophenylalanlne (3) 3 1 (1 34 g. 5 retool), (Irom glycne and Ph2CO). 2 (0 86 g. 5 retool)
and K2CO3 (2 0 g. 15 retool) in MeCN (10 mL) were refluxed with st,rrlng for 1 h Filtration.
evaporallon work up with 1N HCI (3 h) then with conc HCI (6 5 rnmol.6 h reflux), evaporallon and
work up wtth MeOH (100 ml_) and propylene glycol (5 mL) gave 0 85 g of 3 (80%)

276 Name and Unnamed Reactions Name and Unnamed Reacnons
N O Y O R I Chiral homogeneous hydrogenation
Homogeneous chiral hydrogenation of unsaturated alcohols, or carboxylic acids, enamides,
ketonas in the presence of BINAP Ru or Rh complex 8 as catalyst.
loo
9 1 o
1 Noyod, R. J. Am. Chem. Soc. 1980 102 7932
2 Noyod, R. J. Org. Chem. 1986 51 629
3 Noyon, R. J. Am. Chem. Soc. 1986 108 7117
4 Noyod, R J. Am. Cham. Soc. 1987 109 5858
5 Noyod, R. J. Am. Cham. Soc. 1989 111 9134
6 NoyorkR. Chem. Soc. Rev. 1989 18 187
7 Noyod, R. Science 1990 248 1194
60tsuka, S. Synthesis 1 9 91 668
9 Noyod, R. Acc. Chem. Ras 1990 23 345
(R)'(+)-2,2'-BIs(dlphenylphosphlno).l,l'.blnaphthyl (BINAP) (7). 2 To Mg (2.62
g, 0.108 g-at) under N 2 was added iodine (50 rag), THF (40 mL), 1,2-dibromoethane (0.51
mL). 2 2'-Dibromo-l,l'-d/naphthyt I (20 g, 46 4 retool) in PhMe (360 mL) was added
dropse over a pedod of 4 h at 50-75oc. After 2 h stirring at 75°C the mixutre was cooled to
0°C and diphenyl phosphmyl chloride 2 (23 2 g, 98 rumor) in PhMe (23 mL) was added over
30 rain. The mixture was heated to 60°C for 3 h, cooled, quenched with water (60 mL), stirred
at 60"C for 10 rain and the organў layer concentrated to 60 mL After 24 h at 20"C, the
i:xoduct was filtered, stirred wth heptane (45 mL) and PhMe (5 mL), filtered and dried to afford
27.5 g of ) 3 (91%), mp 295-298oc (pure 304-305°C). (:) 3 (65.4 g, 0.1 mol), (1S)-(+)-
camphorsuffonic acid monohydrate 4 (25 g, 0.1 tool) and FJOAc (270 mL) were heated It:)
reflux and HOAc (90 mL) was added to gat a clear solution. Gradually cooling to 2-3oc,
filVatlon and washing (EtOAc} gave 35 3 g of a t:l 1 complex of 3:4 AcOH. The complex was
suspended in PhMe (390 mL), treated wdh water (30 mL) at 60°C and cooled The organic
layer was concentrated to 50 mL and treated with hexane (50 mL). Filtration and dl3qng gave
22.2 g of (R)-(+) 5 (68%), mp 262-263oc, (z04. +399 ° (c 0 5 Phil) (R) 5 (50 g, 76 4 minor),
xylene (500 mL), EI3N (32 4 g, 320 retool) and trlchlorosilane (41 4 g, 304 mmol) under Ar
were heated 1 h at 100°C, 1 h at 120oc and 5 h at reflux 3O% NaOH (135 mL) was added
under stirdng at 60°C, the organў layer was concentrated and the residue treated with MeOH
(200 mL) to give 47 5 g of (R)-BINAP 7 (95%), mp 241-242°C. ўў4..228 ° (c 0.679 Phil).
Methyl (R)-3-hydroxybutanoate (10).4 To Ru(OCOCH3) 2 and (R)-7 (806 rag, 0.975
retool) in CH2C 2 (210 rnL) was added 1.42 N HCI in 90% MeOH 0.41 mL, 2 retool) A/tar 2.5
h sthTing at 20°C the solvent was evaporated to give (R)-BINAP 8 (722 rag) stored under Ar
Catalyst 8 can also be prepared from Ru(COO)CI2, BINAP and TEA, 3 A solution of methyl-3-
Oxobutanoate 9 (100 g, 0 862 tool) =n MeOH (100 mL) was treated wth catalyst 8 (341 rag.
0.429 retool) and hydrogenated at 100 atm and 30°C. Vacuum distillation afforded 97 5 g of
10 (96%), bp 40°C/2 ram, oct) 4 . 24 2 = (neat), 99°1o ee

278 Name and Unnamed Reactions Name and Unnamed Reaction
O L E K 5 Y S Z Y N Amlnophosphor.c acid synthesis
Synthesis of 1-amnoalkanephosphonic and 1-aminoalkanephosphinic acids from ketones or
aldehydes, chlorophosphlnes and carbamates
o ч PC, m-C,H-O-CO-N  (OH)=
NH=
1 2 3 4 (58%)
Me H O El
C=O * E-PC + Ph-CH z O-CO-M-I=  Me-:-. (S%)
H / H, OH
10leksyszyn, J Synthesis 19 78 479
2 Soroka, M Lleblgs Ann. 1990 331
1-Amlnocyclohexylphosphonlc acid (4). t Cyclohexanone 1 (7 35 g, 75 mmol) was
added at 20"C to a stirred mixture of benzyl carbamate 3 (7.55 g, 50 retool) and PCI3 2 (6 87 g,
50 mmol) in AcOH (t0 mL). The mixture was refluxed for 40 min, treated wdh 4 M HCI (50 mL)
and again refluxed for 0 5 h. After cooling, the organic layer was removed and the aqueous
solution was refluxed with charcoal. After filtration and evaporation in vacuum, the residue
was dissolved in MeOH (25-40 mL). The methano solution was treated with propane oxide
until pH 6.7 is reached The precipdate was filtered, washed wh Me2CO and rec=Tstalllzed
from MeOH-water to gNe 7.74 g of 4 (58%), mp 264-265oc.
O L O F $ O N Reagent
The use of vinyl chloroformale for N-deaBqdatlon of tertian/amines, pmtactlon of amino
groups, pmlactlon of hydroxyl groups or formation of 2-kefoimldazoles. Synthesis of vinyl
ca,'bonates by means of fluoro or chloroformates.
oson, R.A. Te'ahedron Left 1977 1567
Olofson, R.A. Teahedron Left 1977 1570
Pratt, PF Te'ahedronLeft 1981 22 2431
Cooley, J.H. Synthesis 19 8 9
Olofson, R.A. J. Org. Chem 1990 55
Olofson, R.A. PureAppL Chem 1988 60 1715
Plperldllle hydrochlorlda (4).2 From a mxture of N-athyipiperidine 1 (I.13 g, 10 mmol)
Ind vinyl chioroformate 2 (1.38 g, 13 retool) in dK:hloroethane at 20 ° are obtained 1.575 g of
ўatoamate 3 (90°/=), bp 63-65"C/0.4 fort. Treatment with excess HCI gave 4 m quantitative

280 Name mu Unnamed Reactions Name and Unnamed Reactions 281
o P P E N A U E R Oxidation
A mtld oxidation of alcohols to ketones, us.'lg metal (hi, K) alkoxides and a ketone.
HOIK I-BuO
HCO "" - Ph
1
1 Oppenauer, R.V. Rec. Tray. Ch.
2 Woodward, R B. J. Am Chem. Soc.
3 Byme, B. Tetrahedron Left.
4 Bersin, T Angew. Chem.
5 Djerassi. C. Org. React.
2
1937 56 137
1945 67 1425
1987 28 769
1940 53 266
1951 6 207
Qulnlnone (2).2 Potassium melal (10 g, 0 25 at g) was dissolved In t-BuOH (200 mL). The
excess of t-BuOH was removed in vacuum until a dry motle powder was obtained. A
suspension of t-BuOK and quinine I (32.4 g, 0.t moO, benzophenone (91.0 g, 0 5 mol) in Phil
(500 mL) was refluxed for 15-18 h under N 2 The cooled mixlure was poured into ice and
extracted wh 10% HCI un,l the HCl was coiodess. The aod extract was washed with Et20 and
dripped with stirring Into NH4OH and ice Extraction with EI20, washing of the extract with bne
and evalx)ration of the extract afforded a total of 3O-32 g of 2 (95-98%), mp 106-108oc.
O P P O L Z E R Chlral reagent
Asymmemc Dlels-Alder reaction, ene reaction, hydrogenation, helogenatlon by means ot
Clllral olatin, such as camphor derivative 1 or 2.
CH=
1 2
4 (8O%) 9g 6% ee v
1 oppolzer, w. Helv Chlm Acta 1 g 8 3 68 2358
20ppolzer, W Helv Chlm. Acta 1984 67 1397
30ppolzer, W. Angew Chem Int. Ed. 1984 23 876
40ppolzer, W. TetrahedronLett. 1986 27 831
50ppolzer, W Pure&ApptChem 1990 62 1241
Dlels-Atder adduct (4). A 1 M soIutK)n of Et2AICI ,n CH2CI2 (70 ml) was added at -76°C to
a mrxture of N-crotonyl sultam 2 (10 g, 35 retool) and cyciopentadlene (5 mi, 77 mmot). Stimng
lhe solutK)n for 18 h at -78°C, subsequent addition of sat aqueous NaHCO3 (100 ml), stlrdng
of the two layers for 15 nn, extracbon (CH2CI2), drying (MgSO4}, evaporation and
crystallization (MeOH) afforded cycioadduct 4 (9 8 g, 80%). mp 184-186°C (endo/exo> 99 5
0 5, diastereomenc excess = 99 6%)

282 Name and Unnamed Reactions
Name and Unnamed Reacnons
O R T O N Haicanlllne Rearrangement
Rearrangement of N*haloanllldes to o- or p-haloanies
BrNCOMe HN-COMe
1
2
10rton, KJ. J. Chem. Soc. 1909 95 1456
20rton, KJ. J. Chem. Soc. 1911 99 1185
3 Richardson, M. J. Chem. Soc. 1929 1873
4 Dewar, M.J.S. J. Chem Soc. 1955 1845
5 Habedleld, P. J. Am. Chem. Soc 1955 87 5502
4-Bromo-2,6-dlmethylacetanlllde (2).3 N-Bromo-2,6-dlmethyfacefandide 1 (1.0 g, 4.11
mmof) was added to boUing water. The resulting solid, after recqstallizatton from Me(-I gave 2,
mp 194- t 95oC.
O S T R O M I S L E N S K Y Butadiene Synthesis
Catalytic butadiene synthesis from ethanol and acetaldehyde.
3SO'C
2 1 3 (35%)
1 Ostrommlensky j.
2 Jones, N E.
3 Egloff, E
J. Russ. Phys. Chem. Soc. 1915 47 1494
J. Am. Chem. Soc. 1949 71 1822
Chem. Rev 19 4 5 36 73
O V E R M A N Pyrro,dlne synthesis
Carbon-carbon bond formation via tandem Mannch condensation, cationic aza-Cope
rean'angement of homoallylamlnes, leading to pyroldmes
I Overman, LE. JAm. Chem. Soc 1979 101 1310
2 Overman, L.E Tetrahedron Left 19 7 9 4041
3 Overman, L E. J. Am. Chem. Soc 1983 105 6629
4 Paowa, A. J Org. Chem. 1990 55 4801
2-Methoxy-2-methyI-N-propyl.3.butenamlne (2).3 A solution of 1 (5 74 g, 40 retool),
obtained from isoprene and NBS-H20 followed by propylamlne, in THF (80 mL), was added at
4"C in 1 h to a suspension of KH (1 6 g, 40 mmol) m THF. After 30 min stlrnng, Mel (5 68 g, 40
retool) was added dropwlse at 4°C The mixture was stirred for 24 h at 20"C, filtered and the
filtrate distilled to afford 5.40 g of 2 (86%), bp 69-70°C, 14 ram. 2 (2.28 g, 14.4 retool) in EtOH
(5 mL) at 0=C was treated wdll HBF4 (1 57 mL, 14.4 mmol of a 9 2 M aqueous solution}.
Concentration and racP/staUlzaton from Phil gave 3.18 g of 2.HBF4 (90%), mp 168-170oc.
3"Acetyl-5-phenyl-l.propylpyrrolldlne (3) 2.HBF 4 (735 rag, 3 mmol), benzaldehyde
(350 rag, 3 3 mmol) and dry Phil (5 mL) was heated at reflux for 5 h. To the cooled mixtore 1 N
NaOH (3 mL) was added, and the aqueous layer was extracted wth Et20. Evaporation and
d=sbltaton gave 500 mg of 3 (87%) as a colorless o=1, 4 3 m=xture of epimers.

284 Name and Unnamed Reactions Name and Unnamed Reactions 285
P A A L - K N O R R Pyrrote Synthesis
Pyrrole synthesis from 1,4-butanedione and amines.
1 2 3(73%) OH
O O H
(NH4k CO3
4 S (40%)
1 PaaI, C. Chem. Ser. 1885 18 367
2 Knott, L. Chem. Ber 1885 18 299
3 Buu-Hoi Ng, P. J Org. Chem. I 9 55 20 639
4 Wasserman, H.H Tetrahedron 197§ 32 1863
-(2,5-Dlmethyl-l-pyrryl)ethanol (3).3 To redishlled 2-amlnoethanol 1 (61 0 g, 1 moo
was added in small podons acetonylacetone 2 (114 g, 1 mol); an exothenT,c reaction
immediately took place, with formation of the product. Vacuum distillation yielded 120 g of 3
(73 6'/.), bp 156-157"C (35 ram} which solidified on cooling, mp 50=C
P A D W A Annulatlon
pyKolines and pyrroles by (4+1) annutaton of 2,3-bls(phenylsu,onyl)-1,3-butadlene and
PhOaS2.  PhOaS .SO2Ph
/ S02Ph + PhCHH. z _...._=..  e
Hh Hh
3 (00%) 4 (S1%)
1 Pa,  Tetrahedmn Left 1 2417
2 Pa, A. Tethedmn Le# 1 39
3 Pa, J Org Chem. 1989 54 810,2862
4 Pa, A J. . Chem. 19 9 0  01
5 PaPa, A O Prep P Int. 1 9 91  
N-Benzyl-3-(phenylsullonyl)-3-pyrrollne (3). 4 A solutn of 2,3-bls(phenylsultonyl)-
13-tadlene 1 (1.22 g, 3 ml) a beiamlne 2 (0 321 g, 3 1) m a 1:1 ure
MH CHI 2 (250 ) was stirr al 20"C r 12 h. A tn of m metxe (3m
s d to the dear tn, and after 1 h stlm at 20 was e@ wdh NH4CI
r=ed solon (50 mL) Usual  up gave 0 897 g of 3 (100% yle}
N-Benzyl-3-(phenylsulfonyl)pyrrole (4). A ln of 3 (0.897 g, 3 ml) a D
(0 1 g, 3  In P (80 mL) w =ўr for 3 h  20  n w dted wdh
CH2CI2 (150 mL), w h 5% NaHCO3 tmn a emrat Chmmatray (siVa
gel - CH2CI2 } affoed 0 579 g of 4 (%).

286 Name and Unnamed Reactions
Name and Unnamed Reactions
P A O U E T T E Olefin Synthesis
Desulfonatlon of sulfones to alkenes (attematNe to Rant)erg-Backlund).
10z 2 (7%)
Me
o, 
Me 3. 100 ° • Me -----l,,-
1 Paquetle, LA. J. Am. Chem. Soc 1976 98 4936
2 Paquetle, L.A. J Org. Chem. 1981 46 4021
3 Paquetle, LA. J Am Chem. Soc. 1975 97 3538
4 Paquetle, L A. Org Syn 1977 57 53
l'4'9,10"Tatrahydro'5,6-banzo-4a,lOa.athanophanantrana (2)2 To 1,4,9,10-
tetrahydro-5,6-benzo-4a,10a-methanothlomethanophenantrene.12,12_dioxide I (1 g, 3 08
retool) In dloxane (40 mL) under N 2 at 0°C was added 1 2 M n-butyl-lithium (2 6 mL) in hexane
"l'he solution (yellow, then brown) was added to a retluxlng slurry of UAIH 4 (0 9 g, 24 retool) n
dioxano (25 mL) and was heated under reflux for 23 h, cooled and treated with sat. Na2SO 4
solution (5 mL). The solid was filtered and nnsed wth hexane The aqueous layer was
discarded and the combined organic phases were washed (bnne) and evaporated. The resJe
was chromatographed (silica gel-petroleum ether) to give 134 mg of 2 (17%) (colorless oil)
P A R H A M Cyclic ether synthesis
Benzoheterocycle synthesis from dlhalldes.
Br .10Ooc Br 
r
1 2
H C -t 00"C
3 4
1 Parham, W.E J. Org. Chem. 1975 41 1184
2 Brewer, P.D Te'ahedron Lett. 1977 4573
3 Bradsher, CK. J Org. Chem 1978 43 3800
4 Bradsher, CK J. Org. Chem. 1981 46 1384, 4600
7"Mathyl-2,3,4,5-tatrahydro-l.benzoxaplne (4).4 1-Bromo-4-(2-bromo-4-
methyiphenoxy)butane 3 (9 66 g, 30 retool) in THF (200 mL) and hexane (50 mL) at -100°C
was treated wilh bllltllium an hexane (33 retool) After 30 rain at -100"C, the mixture was
allowed to warm to 25oc over a pedod of 15 h and was maintained at this temperature for an
additional 6 h. Aqueous work up and distillation gave 3 53 g of 4 (73%), bp 91-97"C (3 5-3.7
tort).

288 Name and Unnamed Reacnon Name and Unnamed Reacnons 289
P A R N E $ Gennal dlmethytatlon
Gem dtmethylaton of cyclohexane denvatNes (wonal dlhalocyciohexanes or
methyicyclohexane) wdh tetmmethylsllane (I'MS) and AIX 3
TMS 2 CH
I AIBr CH=
1 3 (37%)
4 Br  3 (26%)
/cH3 "IbiS. IR U CI
 3 (:'/.)
1 Pames, Z.N ChemComrnun 1980 16 748
2 Pames, ZN Zh OrgKhlm 1981 17 1357
3 Pames, ZN J Org Chem USSR(Engl) 1988 24 291
4 Pames. ZN Dokl Akad Nauk SSSR 1991 317 405
1,1"Dlmethylcyclohexane (3).3 a) To a cooled solution of cls 1.2-dlchloro cyclohexane 1
(58 3 rag, 0 38 retool) =n CH2CI 2 (3 mL) was added TMS 2 (201 mg 2 3 retool) and AIBr3 (6102
rag, 2 3 mmol) After 30 nn a120°C Ihe mixture was poured into water GC analysis Indicated a
37% yield of 3
b) To a mrxture of methyicyClohexane 6 (4 9 g, 50 mmol), t BuCI (6 0 g, 65 rnmol) and TMS 2 (22
g, 250 retool) in CH2CI 2 (30 mL) cooled at 78oC was added AICI3 (10 g, 75 mmol) After 30
stirring at 20°C the mrxture was poured into water (30 mL) and extracted wlh CH2CI 2 The
organic layer after distillation afforded 5 3 g of 3 (80%), bp 119 120°C, n) 0 = 1 4296
P A S S E R I N I Condensation
synthesis of a hydroxycarboxamldes from an socyanrde and an aldehyde or ketone
CHO NC 5=C  "NH""
1 2 3 (32%)
1 Paen,M G Cm I1 1921 51 126
2 Pael,M Cm#aL 1925 55 726
3 8er.J JAm Chem c 1948 70 3712
4 K=s C J Mad Chem 1977 20 1258
5 Lua, WC J O Chem 1981 48 3668
6 UI J Aew Chem 1962 74 9
7 Ecked, H Synthes 1977 332
N-Tort butyl-2-hydroxy-2-(2-pyrldyl)ethanamlde (3). 5 To a mixture ol pyndme 2
cadoxaldehyde 1 (30 g, 0 28 tool) and tart butyl isocyanK:le 2 (10 5 g, 0 12 mol} in chloroform
(100 mL) cooled at 5°C, was added dropwlse wth stlmng trlfluoroacetlc acid (30 g 0 26 mol)
The mtxture was warmed to 20°C stirred wth 1N NaOH (300 mL) for 2  and the organic layer
separated The CHCI3 sofuton was extracted with 1 2 N HCI, the acldў solution was basfled
and extracted with ether After removal of unreacted aldehyde (with NaHSO3} and evaporation
of the solvent the resK:lue (23 g) deposited 8 g of 3 (32%), mp 105-109°C. mp 114 115°C fror
EtOAc

290 Name and Unnamed Reaction
PATERNO . BOCHI 2+2Cydoadditlon
Photochemical 2+2 cyclizatton of carbonyL and oleflns to oxetanes
1 2 (85%)
1 Palemo, E. Gazz. Ch/m./ta/. 1909 39 341
2 B0chi, G. J. Am. Chem. Soc. 1954 76 4327
3 Lange, G.C. TetrahedronLett. 1971 12 715
4 Cadess, H.A.J. TetrahedronLett. 1987 28 5933
P A Y N E Rearrangement
Rean'angement of epoxy alcohols.
\/o\/\_o., ..... o,
1 trans 2 erythro (41%)
t Payne, G.B. J. Org. Chem. 1962 27 3818
2 Swindell, C.S. J. Org. Chem. 1990 55 3
Erythro-4-Methyl-3,4-epoxypentan.2.Ol (2),1 trans-2-Methyl-3,4-epoxypentan.2.ol 1 (3ZI
g, 0.28 tool) was treated with 0.5 N NaOH (150 mL) at 5°C. The solution was kept at 20oc Ior 1 h.
satureSlon with (NH4)2SO 4 (100 g), it was extracted w|h CHCl3 (3 50 mL) and the washed extract
concentrated (max temp 80-85"C). Distillation afforded 13.6 g of 2 (41%), bp 80-81oC, n 5, 1428
v o n P E C H M A N N Dlazo-Olefln Cydoaddition
3+2 olpolar cycloaddltion of dlazo compounds to oleflns. Formation of 2-pyrazollnes
,"B(OBu) + Nm -'CHoCOzEt  /.--B(OBu)2..--.
BOaC.'J', N ",.N N%COaEI
1 2 H 3(44%)
I Pechmann, H.v, ChemBer 1898 31 2950
2 MattesonlDS. J Org Chem. 1962 27 4293
3 Huisgen, R. Angew Chem. 19 6 4 75 616
S-Carbetoxy-2-pyrazollne (3). 2 Dibutyl ethyleneboronate 1 (9 2 g, 50 I)  2 (9.2
g, 50 retool) was kept at 20-30°C under N 2 then heated on a water bath for 12 days. After
0oling to -15"C the upper layer (tnbutyl borate) was removed. The lower layer was washed with
lign)in and treated wdh EtOH (15 mL). Distillation gave 3 16 g (44°/,) of 3, bp 65-700.1 ram.
von PECHMANN- DUISBERG CoumadnSynthesls
Coumadn synthesis from phenols and ethyl acetoacetate.
ч I Ho
°c,,, Me
Me
1 2 3 (83%)
1 Pechmann, H.v.,Duisberg, C Chem. Ber 1883 16 2119
2 Kaufman, K.D. J. Org. Chem 1967 32 504
3 Mlyano, M. JOrg. Chem. 1972 37 259
4 Sethna, S. Org React 19 5 3 7 2

292 Name and Unnamed Reacnons Name and Unnamed Reactions 293
P E D E R S E N Crown Ethers
Crown ether formation and its use in substitutions, oxidatlons,etc
C , _ TsCI 60 o --
O O
1 2 (62%) 15-cmwn-5
Br
Br-CH o2
H CH
Ot. ,c:.= p-c,aqOz O'f--H "C-CH,'C=H, "N° ,
3 4 6
1 Lutdngheus, A. /.Jeb/gs Ann. 1937 528 155
2 Pedersen, C.J. J. Am. Chem. Soc 1967 89 2495
3 Sam, DD. JAm. Chem. Soc. 1972 94 4024
4 Muo Okahara J. Org. Chem.
1980 45 5855
5 Mannlng, M J. Org. Chem. 1981 46 1944
6 Palomo, C. Synthess 198§ 52
7 Gokel, W G Synthess 1976 168
8 Ktakowiak, K E. Chem.Rev 1989 89 929
4-Nltrobenzyl §,6-dlbromopenlcllllnate (5).8 To sodium 6.6-dibromopenlclllinate 3 (11 4
g. 30 rnmol) and 15-ўrowrv5 2 4 (1.5 mL) in MeCN (60 mL) is added 4-ndrobertzyl bromide 4 (6 05
g, 28 mnol) and stilting at 20 ° S continued fOr 24 h. After addition of CH2CI 2 (50 mL) and
washing with water (3x30 mL), the organic solution is dried and evaporated in vacuum to give 8,
rellized from EtOH, 11.5 g of 5 (80%), mp 122.124oc.
P E R K I N Carboxylc Acid (Ester) Synthesis
Synthesis of cycloalkane carboxyhc acids from rz-dlhaloalkanes and diethyl sodiummalonate.
Br + COOEr t .... -- COOC2Hs HCI --CCOH
r/"""' <COOE ------" ,---, cooc,.,---""
2 1 3 (34%)
1 perkln, WH. Chem. Ber 1883 18 1793
2 Perkin, W H. J. Chem. Soc 18 8 8 53 202
3 Dox, AW JAm. Chem. Soc. 1921 43 1366
4 Rice, L.M J. Org. Chem. 1981 26 54
Elhyl cyclohexane-l,l.dlcarboxylate (3). 4 To NaOEt from Na (13 1 g, 0 569 at) in anh.
EtOH (300 mL) was added dropwlse 1 (45 7 g, 0.285 moO, Iollowed by 1,5-dibromopentane 2
(65 6 g, 0.285 tool) The mixture was retluxed for 2 h, the solvent distilled and wafer added
After extraction (Et20), the extract was distilled to afford 20 g of 3 (34%), bp 105-110°C (5 mm).
P E R K I N Coumann Rearrangement
Rearrangement of ўoumanns to benzofurans
5% KOH
--.CI 95% lh , COOH
H
1 COOH 2 (78%)
1 Perkln, WH J Chem Soc 1870 23 368
2 Holton, GW J CherrLSoc. 1949 2949
3 Johnson, I.R. Org React 1942 I 210

294 Name and Unnamed Reacnons Name and Unnamed Reacnons 295
P E R K O W Vinyl Phosphate Synthesis
Reaction of ўў haioketones with tnalkylphosphlte to give ketophosphonate or vlnylphosphate
Br-CH2--C--C-CH= Br + 2 P(OEt) 3 10"
  2h  H-C=C---C=CH=
II
(EtO)=P-O O-P(OEt)=
I 2 6 
3 (98%)
Me
(MeO)P + o =- (Me<:))
1 Perkow W Natunssenschaften 1 952 39 353
2 Perkow W Chem Bet 1954 87 755
3 Boўowilz IJ J Org Chem 1971 38 3282
4 Hennlg, ML. J Org Chem 1973 38 3434
5 Mdsonobu, S J Org Chem 1981 48 4030
6 Liohtenthater, FW Chem Rev 1961 81 607
1,3-Butadlene-2,3-dlol bls (dlethyl phosphate) (3) 4 To a stirred solution of 1,4
dibromo 2,3 butadione 1 (12 2 g, 50 mmol) in Et20 (50 mL) was added dmpwtse
tnethylphosphlte 2 (16 6 g 100 mmol) The reaction mixture was stirred below 10oc for2 h The
solvent was removed and the residue 17 2 g 3 (98%) was Centlhed by IR NMR and MS
P E T E R S O N Olehnatlon
Synthesis of alkenes from ўў Sllyl cal'oanions and carponyl compounds In cases where
separation of -Sllylalcohol dlastereomers (e g 4) can be achieved, pure Z or E oieflns can be
L= + "'SIPh. -.--.-i=... S,Ph.
1 2
2 + Ph Clio -------=- S,Pt.
3 4 PhO. / 5 (46%) E+Z
Ph
BuL THF Bu
Ph CHO - 78 ° Ph S H
1 Peterson, DJ J Organomet Chem 1968 33 780
2 Peterson, OJ J Org Chem 1987 32 1717
3 Peterson, DJ J Am Chem Soc 1975 97 1464
4 Chan, TH J Org Chem 1974 39 3264
5 Mkan K TetrahedronLett 1986 27 4198
8 Ager, D J Org React 1 99 0 38 1
1-Pbenylheptene (4) 4 To stirred n BuLl in Et20 (2 2 mL 5 mmol), was added dmpwlse
inphenylvlnylsllane 1 (1 43 g, 5 mmol) In Ei20 (50 mL) over 1 75 h Benzaldehyde 3 (053 g 5
retool) was added over 5 rain and the mixture was shrred and refluxed for 30 h then poured into
10% NH4Cl (50 mL) The aqueous layer was extracted wth Ei20 Evaporation of the solvent
afforded 2 2 g of a pale yellow Oll which after treatment with n pentane gave triphenylsdanol
(08 g), mp 158 157 5°C The pentane solution after evaporation and distillation afforded 0 4 g
0 4 (46%), bp 46°C/0 01 mm or 94°C/3 mm as a mixture of E.Z isomers (1 1)

296 Name and Unnamed Reactions Name and Unnamed Reactions 293
P F A U - P L A T T N E R Cyclopropane synthesis
Dtazoalkane insertion Into oletins with formation of cyclopmpanes or ring enlalgement of
aromatics to cycloheptatnenes; see also folmation of pyrazolines (yon Pechman).
1 2 (S2%)
1 Pfau, A.S,Plattner, P.A. Helv. Chlm. Acta. 1939 22 202
2 Pfau, A.S., Plattner, P.A. Heir Chim. Acta. 19 4 2 25 590
3 Huisgen, R. Angew Chem. 1 9 5 4 75 5 t 6
4 Gordon, M. Chem. Rev. 19 5 2 50 141
5 Hafner, K. Angew. Chem. 1958 70 419
AZUleli (2) 2 A mixture of 2-isopropyl-4,7-dimethyltndane I (200 g, 1.91 mol) and ethyl
dlazoacetate (50 g, 0.5 tool) was heated for I h at 130°C. Vacuum distillation and recovery of 1
(160 g) gave a brown residue which was heated wth 4(P/o NaOH (40 mL) and EtOH (200 mL).
The uneacted ester was extracted with Et20 and the aqueous solution was acidified to obtain
crude 2, which after distillation afforded 24 g of 2(52%), bp t60-185oc/2ram.
P F I T Z I N G E R Qulnoline synthesis
Qulnoltne-4-carboxyllc acids from isatln and (x-methylene carbonyl compounds.
cOH
o + 
lOO'C
H O Ph Ph
1 2 3 (48%)
CO2H
t PfP, ztnger, W J. Prakt. Chem. 1885 33 100(2)
2 Prltzinger, W. J. Prakt. Chem. 1 8 8 8 38 582(2}
3 Borsche, D. Llellgs Ann. 1910 377 70
4 Henze, H.R. j. Am. Chem. Soc. 1948 70 2622
5 BuuHoi, Ng.P J. Chem Soc. 1949 2882
8 Buu Hoi, Ng. P BulLSoc. Chlm. Fr 1966 2765
2.Phenyl..propoxyclnconlc acid (3) 4 To a solution of 33% KOH (25 mL) were added
isatln 1 (21 05 g, 0.15 tool) and (x.propoxyacetophenone 2 (26 7 g, 0 15 tool}. Enough EtOH
was added to render the mixture homogeneous and this was heated to 100°C lot 48 h After
decoiodzation with charcoal the filtrate was acidified with 50% AcOH and the product 3, mp
216C (40%}, was recwst,zed from dilute EtOH or Me2CO.

2(}8 Name and Unnamed Reaenou
PFITZNER- MOFFATT Oxidation
Oxidation of alcohols to ketones or aldehydes by means of DCC 0M50
occ
p'O2N C'eH4"CH2'OH  P-O2N-CdH4 CHO
1 DMSO
OH 2
O
3 4 (90%)
Pfitzner K E. Moffatt J G J Am Chem So(: 1963 85 3O27
Pfitzner K E. Moffatt. J G J Am Chem So(: 1965 67 5661.5670
Johnso. C R Tetrahedron Lett 1965 25 2101
Schobert R Synthesis 1987 741
Epstein WW Chem Rev 1967 67 247
pNItrobenzaldehyde (2) 1 To a SOlUtmn of p-r, trobenzyl alcohol 1 (0135 g 1 mrnol) In
DMSO was added dlcyclohexylcarbod,mide (DCC) (0 618 g. 3 retool) TLC indmated
quantltallve oxidation 2 was olated as the DNPH derivative m 92% yield mp 318 317oc
4-Androsten-3,17-dione (4) 2 A mixture of testosterone 3 (29 nj 0 1 mrnol) and DCC
(62 mg 0 3 retool) In DMSO (0 5 mL) was St.Ted with H3PO4 (4 8 mg 0 05 mrnol) After 2
h an eddltonal amount of DCC (20 rng, 0 1 retool) was added Stlmng was continued for a
few hours then the solvent was evaporated (45=C) and the rescue chromatographed by
preparative "LC (silica gel. CHCI 3 EtOAc 41) to gNe 28 mg of 4 (98%)
Name and Unnamed Reacnon
P I C T E T - H U B E R T - G A M S tsoqulnoline Synthesis
Isoqulnolmes from phenethylamtdes phenanthndlne from o acylammoblaryl wth POCI3 -
SnCl4 s
CHO A CHO A
CH _.OC,= 
2 (97%) _/
1 PIctet A Hubert Chem Bet 1896 29 1162
2 Plctet A Gains A Chem Bet 1909 42 2943
3 Falck. JR J Org Chem 1981 46 3742
4 Whaley MW Org React 1951 6 151
5 Boyer J H Synthess 1978 205
Papaverlne (2) 3 POCI 3 (423 nj 3 mmol) was added dropwlse to refluxtng 1 (423 nj 3
retool) in MeCN After I h the nxture was poured into ice water washed (Et2 O) has,fled (2N
NH4OH ), extracted with EtOAc and chromatographed to give 371 rng of 2 (87%)
P I C T S T - S P E N G L E R Isoqulnoline Synthesis
Isoquinohne synthesis of phenethylamlnes and pyruvlc acid derivatives
HO HO
3 4 .. h
6 Pictet A Spengler F Chem Bet 19 1 1 44 2030
7 HudlK:ky T J Org Chem 1981 46 1738
8 Bates HA J Org Chem 1986 51 3061
9 Govmdachan. TR Org React 1951 6 151
10 Valentine D Synth 197 8 329

300 Name and Unnamed Reactions
Name and Unnamed Reactions 301
PILLOTY . ROBINSON Indolesynthesis
Indois (carbazole) synthesis from azines, see also Fischer.
1 Pillory, C. Chem. 8er. 191 0 43 489
2 Robinson, R. J. Chem. Soc. 1918113 839
3 Poavtc, H. J. Org. Chem. 197 4 39 2575
4 Robinson, B. Chem. Rev. 1 969 69 227
N-Acetyloctahydrocarbazole-l,2,3,4,5,8,7,8 (2).3 Cydohexylketazine 1 (4.8 g, 25
retool) and TsOH (0.5 g) In Ac20 (25 mL) were refluxed for 1 h. Evaporation of the solvent In
vacuum and cP/stalllzation of the rasidue from MeOH:H20 afforded 3.7 g of 2 (64%), mp 72-
74oc.
P I N N E R Imino ElMer Synthesis
Synthesis of imino ethers, amldlnes and ollho esters from ndntes.
Oў:l EtOH NH
CH--C%/ CH=_ c/
PhMe -
NH.HCl M'kJ %NH.HCl
1 ._ 2 (:r,)  (S,)
H
4 f'/7%) CH=-C(OEt,
1 Pinner, A. Chem. Ber. 1877 10 1889
2 Rapoport, H. J. Org. Chem. 1 981 46 2465
3 Roger, R. Chem. Rev. 1961 61 179
4 Pompaert, J. Synthesis 1972 622
P I R K L E Resolution
1.(1-Naphthyl)elMyl socyanate 2 for chmmatographў resolution of alcohols, hydmxy esters
Ihlols via diastereomenc dedvatwes.
Me M CF
.--,., ,co .--o.
ч --
(R)- 1 (R)- 2 (98%) 3
CF O . Me CF
(RR)Sa (75%) + (RS)Sb {R)(-) 6
1 Pldde, WH J Org Chem. 1974 39 3904
2 Pidde, WH. J. Org. Chem. 1979 44 2169
3 Ine. H. J. Chem. Soc PerktnTr I 1989 1209
(R)-(-)(1-Naphthyt)-2,2,2-trlftuoroethanol (6). I (R)-(ч)-l-(1-Naphthyl)ethylamme 1
(1713 g, 0 1 mo o in Phil (200 mL) was treated with dry HCI to give the 1 HCI The mixture was
diluted with PhMe (100 mL), phosgene was bubbled in and after a few  It was heated to
reflux for 4 h. Distillation gave 19.06 g of R-{-)- 2 (96 3%), bp 106-108oC (0 16 ram),  -
"50.5 °. Racenac 3 (6 20 g, 0 27 reel) and (R)-(-) 2 (5 34 g, 0 27 mo o were mixed and heated to
80°C Ior 65 h, until the NCO band at 2260 cm 1 disappeared. Cinematography on alunana
(Phil) gave a maloў fraction, 4 34 g of 5a (75%), mO 139 7-140 6"C (Phil)
5a (4.32 g, 10 1) was added to NaOEt (2 5 g Na and 3O mL EtOH) and relluxed for 30 nan.
Evaporation, neutrakzaton, extraction with CH2Cl 2 and chromatography of the residue (s|llca
CH2CI2) gave 2 17 g of 6 (95.7'/.). Oishllaton altorded 9 mO 52-53"C, x - +25.8 °

302 Name and Unnamed Reactions Name and Unnamed Reactions
P 0 L 0 N O V S K Y N-oxide Rearrangement
Conversion of heterocycllc N-oxides to cў-acetoxyheterocycles
CI N,,.. 7h, A
Ph
1 2 (59%)
o"
1 Polonovsky, M. Bull. Soc. Chlm. Fr. 19 2 7 4 f 1190
2 Bell, S.C. J. Org. Chenz 1962 27 1691
3 Stembach, LH. J. Org. Chenz 1985 30 3576
4 Laionde, R.T. J. Am. CherSoc. 1971 93 2501
5 Glerson, O. Org. React. 1990 39 85
3-Acetoxy-l-acetyl-7-chloro-2,3.dlhyd ro-5-phenyl.1 H-benzo-l,4-dlazeplne
(2). 2 A solution of 7-chlom-2,3-dlhydmol-acetyl-5-phenyl-lH-1,4-benzodlazeplne-4.oxtde 1
(7 0 g, 22 rnmol) in Ac20 (60 mL) was refluxed for 7 h. The solvent was removed m vacuum and
the residue was triturated with Et20. The crystalline product after recnJstallization Imm hexane
CH2CI2 gave 4.6 g of 2 (59%), mp 177-179eC.
POMERANZ - FRITSCH . SCHLITTER . MULLER
I soqulnollne Synthesis
Isoqulnoline synthesis from amrnatic aldehydes and an amlnoacetal (Pomeranz-Fritech) or from
phenethylarnines and glyoxal acetal (Schlltter-Mutler).
CliO + CH(OEt)2I A MeO
H=N-CH 2 --.--=,..
o.. .=...c. ' H,so._._..,
1 2 3 (99"/,,) 4
CH(OEt) 2
Ph,,NH 2 + o@H  CH(OEt)2,!
t h PHv,
7 (Ss%) e
1 Pomeranz, C. Monatsh. 189 3 f 4 116
2 Fnlsch, p. Chem. Ber. 1893 26 419
3 Whde, J.O. J. Org. Chern. 1967 32 2689
4 Popp, F.D Chem. Rev. 1958 58 328
$ Gensler, W J. Org ReacL 1 9 51 6 192
Q Schter, E., Mueller,I He/vChmtActa 1948 3f 914,1119
7  AJ. J.ChertSoc. Perk.in Tr. 1974 2185
|'8"Olmethoxylsoqulnollne (4),4 2,4-Olmethoxybenzaldehyde 1 (3 6 g, 22 retool) and 2-
mlinoacetaldehyde dtelhylacetal 2 (3 48 g, 26 retool) .1 Phil (50 mL) was refluxed for 2 h. The
Iolvent was distilled in vacuum to gwe 6.14 g of 3 (99%). CnJde 3 (2.84 g, 10 retool) was added
b cooled 75% H2SO4 (20 mL) and stimng was continued for 3 h at 0=C and for 3 h at 20 °
0Uenching with water, extraction wth Et20, chromatography on neutral alumina (hexane-PhH)
and reCrystalhzatlon from hexane-PhH gave 0 142 g of 4 (7 5%), mp 125-126C

304 Name and Unnamed Reactions
Name and Unnamed Reactions
P O S N E R Tdoxane synthesis
Reaction of tdethylsl hydmtdoxlde with electron-rich olefins to give dioxetanes that react
IntramoleoJlarly with a keto group in the presence of t-butyldimethyl stlyl triflateto afford 1,2,4-
Inoxanes; also oxydatlve cleavage of alkenes Also used in ўdeavage of olefins
O  O O =
-7'C 
1 OMe 2 3 (S8%)
 ES<X)OH LAH ./,".,OH
MeO MeO (8O%)
1 Corey, E.J J. Am. Chem. Soc. 1 g 88 106 2472]
2 Posner, G.H. J. Am.Chem. Soc. 1987 109 278
3 Posner, GH. J. Org. Chem. 1989 54 3252
4 Posner, G.H. TetrahedronLett. 1991 32 4235
Trloxane (3).4 Tnethylsllyl hydrotnoxide was prepared, in situ, by rapid addition of
tdethylane (0.52 mL, 3.2 retool) Into ozone-saturated methylene chloride (80 ml) at o78°C.
To this freshly-prepared solution of EI3SIOOOH (80 ml, 3 2 mmol) at -78C was immediately
added methoxy vinyl ether 1 (63.7 rng, 0 32 retool) in CH2Cl 2 (3 mL) over 10 sec under N 2
After 30 rr,n stlmng was added pre-cooled (-78oc) TBDMSO'rf (0 080 mL, 0 35 mmol) m
CH2CI2 (1 mL) over 1 rnin. After 5-15 mtn stimng at -78o(3, TEA (0.68 mL, 4 9 mmol) was
added, the mixlure was kept at -20°C for 1 h then warmed to 20'(3. Chromatography
(EIOAc:hexane 2.98) gave 42 mg of 3 (58%), mp 68-69oc (from hexane).
P R E V O S T - W O O O W A R D Otefln Hydmxylation
Odunctional=zaton of alkenes wth dine and lver (or sodium) cadxylates.
NH PhCOOAg NH
 A '- Ph
1 2 (28%)
3 4 (65%)
1 Prevost, C. CR 1933 196 1129
2 Smtssman, E E J Org. Chem. 1970 35 3532
3 Johnson, RG Chem Rev 1956 56 261
4 Wilson, C V Org. React. 1957 9 350
5 Woodward, RB J Am Chem. Soc. 1958 80 209
6 Lwowakl, W Angew. Chem. 1958 70 490
4(a)'lsopropyl-6-benzoyloxymethyl.SH,6H.fu ro[2,3.d].&l,?.2,4.(3H).
Pyrlmldlnedlone (2).2 A suspension of sliver benzoate (11.50 g, 50 retool) in Phil (200 mL)
was treated with 12 (5 35 g, 25 retool) in Phil (100 mL). After 15 rain stirring, 5-isopropyl-5-
allylbarbdudc acўl 1 (5 25 g, 25 retoOl) m hot Phil (200 mL) was added and the mixture was
refluxed for 2 h. Cooling, rdtration, concentration in vacuum and chromatography of the rasldue
on sllca gel (CHCI3) afforded 2 28 g of 2 (28%), mp 170-172oc (Me2CO. petroleum ether)

306 Name and Unnamed Reactions Name and Unnamed Reactions 307
PRINS - KRIEWITZ Hydroxymethytan
Acid catalyzed hydroxymathylation of alkenes. 1,3-Dioxane symllis.
+ o  +
2 1 3 (22%) 4 (2%)
o  CH=Cl
--C + 1  J
S 6 (49.)
1 Kriewitz, O. Chem. Ser. 1899 32 57
2 Pdns, H. Chem. Weeckb/ad 1919 16 84,1072
30olby, LJ. Org. Chem. 1983 28 1456
4 Adam, O.R. Synthesis 1977 661
5 Andersen, N.A. J. Org. Chem. 1985 $0 4144
6 Alundale, R. Chem. Rev. 1952 51 5O5
3-Oxablcyclo[4,3,0]nonane (3); trana-6-hydroxy.cls.3.OXSblcyclo[3,3,1].
norlalle (4).3 Paraldehyde I (1.83 g, 61 retool) in AcOH (5 mL) and one drop of H2SO4, was
heated under stlrdng to S0=C. 3-Hydmxymethylcydohexene 2 (S.0 g, 44 retool) in AcOH (5 mL)
was added dropwise and the mixture was heated for 2 h at 70 °. The cooled mixture was diluted
wdh water, neutralized with Na2CO 3 and extracted with CHCI3. FractlonaJ distillation gave 6.11 g
of 3 and 4 in a ratio of 22:2 (GC) as well as other products.
4-Chloromethyl-l,3-dloxafle (6).4 Nlyl chiodde 5 (600 g, 8 tool) was added over a period
of 1.5 h to an ice cooled stirred mixture of I (300 g, 10 tool) and sulfud acid (180 mL). Nter 3O
rain the mixture was poured into ice water, the organic layer was washed with 5"/,, K2CO3, dried
and distilled to give 300 g of 3 (45%), hi:) 83-86°C (22 ram).
P S C H O R R Arylation
Fontbn of polycyclics from a dlazonlum salt. Intramolacular Cu catalyzed a,-ylation of
dlazonium salts (see Gomberg - Bachmann).
1 2 (4o%)
1 Pschorr. R. Chem 8er. 1900 33 1810
2 Hey, O.H. J. Chem Soc. 1949 3162
3 Kupchan, S.N. J. Org Chem. 19 7 3 56 405
4 Leake, P.N. Chem Rev. 1956 56 27
5 DeTar, OL.F. Org React. 1957 9 409
6 GokeI, G.W. TetrahedronLeў 1980 21 4141
Phenanthren-9-carboxylk: acid (2). 3 A solution of o-aminophenyk:thnamio acid 1 (1
g, 6 retool) in HCI (3.3 mL) and water (100 mL) was diazofb:ed with NaNO2 (0.7 g, 10 retool) in
water (40 mL). To the dtazonium salt was added copper bronze (1.0 g), the mBdure was heated
on a water bath to complete the reaction The whde solid was filtered, dissolved in ammonia,
filtered from insoluble matedal and the llltrate was acidified. Crystallization from .acOH gave 0.5
g of 2 (40%), mp 250-252°C

308 Name and Unnamed Reactns Name and Unnamed Reactions 309
P U M M E R E R Suloxide Rearrangement
Rearrangement of a sulfoxide to an oPacetoxysulflde.
o o EoIO I
Bo\ II I! AoO
EtO/p  CH2"S  CHs Me,SO3H A  EtO / P  IOCOcH=CH  S-Cell $
1 2
1 Pummerer, R. Chem. Bet. 1910 43 1401
2 Johnson, CR. J. Am. Chem. Soc. 1969 91 682
3 Dlnizo, St. D. Synthess 1977 181
4 ishibashi, H. J. Chem Res. 1987 296
5 Takahashi, T. J. Chem. Soc. Perlmll 1991 1667
6 DeLuccht, O. Org. React. 1991 40 157
(x-Acyloxy-(x-(dtethoxyphosphlnyl)methyl phenyl Sulfide (2). 3 To a solution of
(dlethoxyphosphinyl) methyl phenyl suloxlde I (27S rag, 1 retool) and Ac20 (204 rag, 2 retool)
In dry CH2CI2, was added methanesulfonio acid (24 mg, 0.25 retool). The solution was refkJxed
for 3 h, cooled, diluted with 5% Na2CO3 (25 rnL) and extracted with EI,20. Purification by
preparative TLC (silica gel F 254, eluent Et20) gave 225 mg of 2 (72%), n) 0 . 1 5103.
RAMBERG - BACKLUND OlefinSynthesis
Conversion of dlalkyl sulfones to aJkenas by rearrangement of (x-halosuEones wth base (via
ff, arenedioxides).
1 Rambelg, L, Backlund, B. Ark. Kem. lneralGeol. 1940 13A 50
2 Paquette, L. J. Org. Chem. 1981 46 4021
3 Opltz, G. Angew. Chem. 1963 77 411
4 Paquette, L. Org. React. 1977 25 1
1,4,9,10-Tetrahydro-5,6-benzo-4a,10a-ethenophenantrene (3). 3 To 1,4,9,10-
tetrahydroo5,6-benzo-4a,10a-methanothK)methanophanantrene 1 (14.6 g, 50 retool) were
added N-chiorosuccmimide (NCS) (6 72 g, 50 5 retool) and dry CCI4. The rnedure was refluxed
under N 2 for 29 h, cooled, filtered, and evaporated to gwe a mixture of isomeric (x-
chlorosulfides. To this product in CHCI 3 (200 mL) at -23°C was added droe 0.624N
ethereal monoperphthalic acK:l (163 mL). After 10 h at 20 °, work up gave an Isomeric mixture of
ўў-ўhioro sultone 2.
Sulfone 2 dissolved .1 dloxane (250 mL) was treated with t-BuOK (35 1 g, 0,313 tool) under N 2
at 0°C, then heated to reflux for 20 h Dilution with water and chromatography on silica gel
(hexane) gave 5 13 g of 3 (40%) as a yellow

310 Name and Unnamed Reactions Name and Unnamed Reactions
R A P P - S T O E R M E R Benzofuran synthesis
Benzofuran synthesis from sallcylaldehydes and a-haioketones
4 (67%)
1 Rapp, E. Gazz. Ch/m.//a/. 18952511 285
2 Stoermer, R. I.Jebo$,4nn. 1900 32 331
3 Buu Hoi, No. p. J. Chem. Soc. 1957 2593
-Chloro-2-(4-hydroxybenzyol)benzofuran (4).3 A mixture of 5-chlomsallcylaldehyde
1 (15.0 g, 0.096 tool), (x-bromo-p-rnethoxyacetophenone 2 (22.0 g, 0 096 tool), KOH (5.3 g,
0.096 tool) In EtOH (150 mL) was heated to reflux to give 10 g of crude 3 (35%).
The crude 3 (10 g, 0.0325 tool) was heated In pyridine hydrochlonde for 30 rain The cooled
rr, bdure was stirred with water, the product was filtered and purified via  sodium salt (NaOH
then precipitation wth HOAc). Recstallizatlon from aqueous EtOH afforded 6 g of 4 (87%), mp
238°C.
R E E T Z Ti alkylaticn
Chemo and dastereoseleclve addition of alkylttanlum reagents to aldehydes.
,.. /. =,..
,,,-c,c c__..._..j, ,,.-:'cc---, + ,,...:'cc---.
1 2 (821) 80 20 3
1 Reetz, iT. Angew. Chem. lnt. Ed. 1980 19 1011
2 Reetz, M.T. Chem. Ind. 1981 541
3 Reetz, M.T. Tetrahedron Lett. 1981 4691
4 Reetz, MT. Angew. Chem. lnt. Ed. 1982 21 96
5 Posner, GH. Tetrahedron 1984 40 1401
6 Reetz, M.T Angew. Chem. lnt. Ed. 1984 23 566
Threo and erythro 2-phenylbutan-3.01 (2) and (3). 1 A cooled solution (o50oc) of 2-
phenyipropionaldehyde 1 (2 7 g, 20 mmol) m dnj CH2CI 2 (50 mL) Is added dropwise wdhin 20
mm to a mixture of dimethyltdanlum dichlonde (prepared from dimethyl zinc and TiCI4 hi CH2CI2)
(298 g, 20 retool) in CH2CI 2 (100 mL). After 1 h the mzxture =s poured into ice water and b'eated
wllh dll. HCI until the preclpdate dissolved. The organic phase ts separated and the aqueous
phase extracted 3 times with CH2CI 2 The combined organic phases are dded (MgSO4) and the
solvent removed to give 2 and 3 in a ratio of 80 20 (GC) By distiitatlon (kugelrohr) one obtains
2.45 g of 2 and 3 (82%) (80°C 1 tort)

312 Name and Unnamed Reaction
Name md Unnamed Reaction
REFORMATSKY . BLAISE 7rcalkylatlon
SyrV, hesis o1 -hydroxyasters from carbonyl derivatives and o.-haloesters wa a zinc reagen!
(Reformatsky). Synthesis of [}-ketoesters from niffiles and (xqlak:)esters via a znc reagent
(Blaise).
C-CHO + Br-CHzCOOB  C.CH.CHz.COOE t
1 2 B(OEI}3 OIH 3 (95%)
HO F
40SIMe, Zn ultrasound  C - CHF o cooer 
0 SIMe= S Ph
6(S2%)
1 Reformatsky, S.N. Chem. Ber. 1887 20 1210
2 Ralhke, M.W. J. On3.ўhem. 1970 35 3966
3 Rathke, M.W. Org. ReacL
1976 2Ј 423
4 Blaise, E. C.R. 1901 13Ј 478
5 K'azume, T. $),nthes$ 1986 855
6 Klsht, y. J. Org. Chem. 1983 46 3833
7 Toda, F. J. Org. Chem. 1991 56 4333
8 Fuerster, A. Synthes$ 1989 571
Ethyl 3-phenyl-3-hydroxyproplonate (3).2 To zinc powder (6 54 g, 100 m at.) in THF
(20 mL) under N 2 was added I (10.6 g, 100 ml) 1THF (25 rnL) and B{OE)3 (25 rnL). Under
stimng 2 (121.1 g, 100 retool) was added at once and afer 12 I1. con NH4Cl (25 mL) and gly-
cerol were added. Extractfon (Et20) and disffilation gave 18.5 g of 3 (95%),
(x-Phanyt-y-fluorotetronlc acid (6). s To Zn powder (3.92 g, 60 m at.) and cyanohydnn 4
(5.1 g, 25 retool) in THF (5 mL) was added (-fluorobromo acetate 5 (3.7 g, 20 retool) in THF (5
mL). NI was irradiated in an ultrasonў bath cleaner (32 KHz, 35 W) for 2 h, quenched in ice (300
g) and H2SO 4 (20 mL) and kept for 24 I1 at 20oc. Extraction with EIOAc drying evaporatfon of
the solvent and recrystallizatlon afforded 2.4 g of 6 (62%), mp 102-105oC.
REGITZ Dlazo tmnster
Synthesis of diazo compounds from active methylenes with tosyl azide (dlazo trans/er).
OH o o
1 3 (100%)
p -TsN NC. I.CN Et.l
NC-CH=-CN   NO.t .CN
N N=N-N*E
pTsN-j
(R-,SOzH2  (R SOt'-N'2
1 Regitz, M. Angew Chem. In Ed. 19 8 7 6 733
2 Regitz, M. Chem. Ber. 1984 97 1482
3 Ledon, H. Synthests 1972 351
4 Ledon, H. Synthests 1974 347
S Kotaswar, Rao Y Indian J Chem. 1988 25b 735
S-01azo-6,7-dlhydro-2,6,8.trlmethyl.4(SH)-benzofuranone (3).S To 6,7-
dihydro-S-formyl-2,6,6-trlmethyl-4(SH)-benzofuranone I (774 mg, 3.76 mmot) in CH2CI 2 (5
mL), was added p-toluenesulfonyl azide 2 (740 rag, 3 76 nlnl) in CH2CI2 (5 mL), followed by
1,8-dlazoblcyclo [5,4,0]-undec-7-ene (DBU) (576 rng, 5.64 retool). The mixture was stin'ed for
15 mln at 30°C, poured into 10% KOH (20 mL), the oRlanў layer was separated, washed (HCI,
water) dried (MgSO4) and evaporated fo gwe 765 mg of 3 (100%), mp 102o103°C, (from
hexane); decomposed slowly at .

314 Name and Unnamed Reactions Name and Unnamed R eacnons 315
R E I M E R - T I E M A N N Phenol Formylation
Formylation of phenols with CHCl3-base (dichiorocarbene)
(4o%)
Clio
1 2 3
I Relmer, K.
2 Relmer, K., Tiemann, F.
3 Bird, C.
4 Newmann, R.
5 Wynberg, H.
6 Wynberg, H.
Chem Bet. 1876 9 824
Chem. Ber. 1876 9 1285
Chem &Ind.(London) 1983 21 827
Synthesis 1 98 6 569
Chem. Rev 1980 60 169
Org. React. 1982 28 1
2- and 4-Hydroxybenzaldehyde (2) and (3). 4 To a mixture of sodium phenolate 1 [12 2
g, 0 2 mot), polyethylene glycol (PEG 400), CHCI3 (71.7 g, 0 6 mol) and PhMe (50 mL.) was
added 50% KOH (80 mL.) dudng a penod of 30 rain. Stlmng was continued for an additional 30
mln The solvent was removed and the residue aCldtfied with 2N H2SO 4 (300 mL). After steam
distillation and recrystallization, 9 76 g of 2 and 3 (40%) was obtained: mp of 3" 118-119°C
REISSERT - GROSHEINTZ • FISCHER CyanoamlneReacton
Synthesis of aldehydes or alkaloids from acid chiondes wa 1-cyano-2-acylisoqulnoline or 2-
cyanoqulnohne intermediates
3s/H0i HMPA
_,,.CH2C I N O N O
1 Relssert, A Chem Ber. 1905 38 1608, 3415
2 Grosheintz,J M, F=scher,H 0 L J Am Chem Soc 1941 63 2021
3 McEwen, WE J Org Chem. 1981 46 2476
4 Mosettig, E Chem. Rev 1955 55 511
5 Popp, F D Synthests 1 970 591
6 Popp, F D Bull Soc Chum Belg. 1 9 81 90 609
8,6,13,14-Oldehydro-9-oxoberberlne (4). 3 1 [2 5 g, 20 mmol), KCN (6 5 g, 100 retool)
CH2C12 (30 mL), water (16 mL) and benzyltnethylammonium chionde (176 rag, 0 77 mmol) were
stlrred at 0°C and 2 (7 34 g, 39 mmol) in CH2CI 2 (I 0 mr.) was added over 50 mln. Extraction wdh
CH2C12 and evaporation gave 5 6 g of crude 3 (93%) Chromatography afforded 4 81 g of 3
(80%), mp 136-I 37°C LDA (from 134 mmol BuLl n 25 mr. THF) was stirred for 15 rain at 20"
and added over 40 rain to 3 (2 0 g, 65 mmol) in THF (125 rnL) and HMPA (50 mL) at -78°C Aer
26 h at 2O ° the mxture was poured znto ce water (1500 ml_) and filtered to obtaln crude 4 (I
g), 350 mg of 4 from MeOH and from the mother liquor total of 710 mg (44%), mp 144-I 46°C

316 Name and Unnamed Reactiona Name and Unnamed Reactiona 317
R E P P E Acetylene Reactxms
HC =:== CH + CHaO  HO- CH- CH. CH.CI. O.
1 Reppe, W. LJeblgsAnn. 1948 560 1-104
2 Reppe, W. F-xpenentla 1 9 4 9 5 93-108
3 Reppe, W. Uebigs Ann. 1 953 582 1-133
4 Reppe, W. OeblgsAnn. 1955 596 11-20
5 Lutz, E.F. J.Am. Chem. Soc. 1961 83 2552
Cyck:loCtalelraene (2).2 A Cooled (0.100C) solution of NICI 2 in EtOH was treated wdh 10%
elanolc HCN. After 12 h at 0" the NI(CN)2 catalyst was filered andwashed. ToNi(CN) 2 (20 g)
and calcium cadolde (50 g) In THF (2000 mL) under N 2 at 5 arm. acetylene was introduced at 15-
le: and the mixture was heated to 30-500C while acetylene was introduced from time to
• After removal of the catalyst, distillation afforded 320-400 g of 2, bp 141.142oc.
Benzene (3).s AIEt3 (3.4 g, 30 mmol) m n-heptane (200 mL) was treated with TICI4 (1.9 g, 10
minor) in n-heptane (5 mL) under N 2 vnth efficient stirnng. Acetylene 1 was bubbled thn)ugh a
solution Of catalyst (30 roL/mln). The temperature of the mixture rose slowly from 22°C to 30°C
After 5100 mL of 1 was passed through, the catalyst was removed and 3 was distilled (50%).
von RICHTER .s.roroaticCaJtx)xyation
Reac6on ol m- and p-nltrohalobenzenes with CN" leading to o- and m-halobenzolc acids with
loss of the NO2 group.
Bt 1 Br 2
NO= N" C=
Br v Br
O,, .-O O-N. O'C-O COOH
1 Richter, v W. Chem. Bet. 1 871 4 21
2 Richter, v.W. Chem. Ber. 1875 8 1418
3 Bunnett,J E. J Org. Chem. 1 950 I5 481
4 Bunnett, JE. JOrg. Chem 1956 2I 944
5 it)neRasa, K.M JOrg. Chem 1963 28 3240
6 Huisgen, R Angew Chero• 1960 72 314
3-Broroobenzolc acid (2). 4 A mixture of 4-nltrobromobenzene 1 (4 0 g, 20 mmol) and
KCN (2.6 g, 40 mmol) tn anhydrous EtOH was heated to reflux for 1-2 h After work up there
was obtained 0 4 g (10%) of 2, mp 155-158°C

318 Name and Unnomed Reactiona
R I C H T E R - W I O M A N - S T O E R lUl E R Clnnoline Synthesis
Synthesis of cinnolinas from substituted anilines via diazonlum salts.
NaNO 2
0 1
OH 2 (5.%)
3 4
1 Richter, v.W. Chero. Bet. 1883 I6 677
2 Scofleld, K. J. Chem. Soc 194 9 2393
3 Leonard, N.I. Chero. Rev.
1945 37 270
4 Widman, O. Chero. Bet. 1884 I7 722
5 Sloermer, R. Chero. Ber. 1909 42 3115
6 Scofleld, K. J. Chem. Soc.
1945 512
7 Simpson, J.C.E.
J. Chero. Soc. 1947 808
4"Hydroxy-3-phenylclnnollne (2).2 2-Amlnotolane 1 (40 rag, 0 2 romor) In 32% HCI (1
mL) at 0"C was diazotized wdh NaNO 2 (15.2 mg, 0.22 minor), kept overnight at 20 °, and heated
to 95oC. The mixture was diluted with water (5 ml..) to afford 25 mg of 2 (55%), mp 260-261°C
4"Hydroxy-8-cyanoclnnollne (4).8 A COOled suspension of 3 (1.0 g, 6 1 rumor) in 2N HCI
(15 mL) was treated wlth 15% NaNO 2 (15 mL) under stlrnng The mixture was heated on a water
bath for 1 h, COoled, filtered and the crude 4 was disso/ved in Na2CO3 solution, treated with
Notate charcoal HOAc precipitated 4 Recrystallizatlon from EtOH afforded 4, mp 284-285oc
R I L E Y Selenium Dioxide Oxidation
Oxidation of aldehyde or ketones to 1,2-dlcarbonyl compounds with SO2 (sometimes
oxidation to o.,ўlnsaturated ketonas).
O O
1 2 (2o/.)
O O
o fro',.)
I Riley, H.L J Chem.Soc. 1932 1875
2 Schaefer, J.P. J. Am. Schero. Soc. 1933 66 1668
3 WaJnG.R. Chero. Rev. 1945 36 235
4 Rabjohn, N. Org. React. 1978 24 283
5 Shaplas, K.B. JAm. Chem. Soc 1978 98 300
Cyclohasalte-l,2,,dlone (2). I A solution of SeO2 (56.0 g, 0.5 tool) in EtOH (300 mL) was
added dropwise in 2 h to heated (70-80oc) cyclohexanone 1 (50.0 g, 0.5 tool). Heating was
continued for another 2 h, the solvent was removed by distdlatlon and Se was separated and
washed with Et20. Vacuuro distillation of the residue gave 40 g of 1 and 2. SeparaUon of 2 by
extraction with 10% KOH froro an Et20 solution, acidification of the aqueous solution with ice-
(:ooled HCI, saturation with NaCI and extraction wdh Et20 gave 11 g of 2 (20%), bp 96-97"C (25
ram). bis phenylhydrazone, mp 152°C.

320 Name and Unnamed Reacnons
Name and Unnamed Reacnona 321
R I T T E R Amafn
Ac cam/yzed reaction of nlmles wlh aikenes or alcohols 1o afford amides
1 RIIter, JJ JAm Chem Soc 1948 70 4045
2 Rltter, J J J Am Chem Soc 1 9 S 2 74 763
3 Balaban, A. J Org Chem 1955 30 879
4 Wold, R.A J Cj Chem 197 3 38 3099
5 roatul,n, VG Bull Acad Sct USSR 1988 35 356
6 Knmen, LI Org Reect 1869 17 215
7 Meyers, AI J Org Chem 1973 38 36
Threo-2-Acetamido-3-bromobutane (3) 4 To threo- 1 (15 3 g, 01 tool) in ice cooled
MeCN 2 (12 3 g, 0 3 tool), was a<ded under stimng H2SO4 (70 7 g, 0 7 mol) over 30 mm The
solutoll was warmed to 20 °. kept for 3 h at 35°C, and poured into me waler (300 mL) Na2CO3
(20 g) was added in Ix)rtlons and the solution was stirred for another 5-10 rain E,xlractx)rl wlth
Ef20, dryzng and evaporaticn of the solvent gave 15 7 g, of 3 (81%)
R O B I N S O N Annulatlon
Fusion of six membered nngs by reaction of cyclanoes wllh vinyl ketones (base or acid
catalyzed), a tandem Michael addition aldol condensation
+ 
1 2 3 (49%)
1 Rolnson R J Chem. Soc 1937 53
2 Gawey, R E Synthes+s 1976 777
3 Huffman, JW J Org Chem 1985 50 4255
4 Brewster J C C>rg React 1 9 53 7 113
10-Methyl-2-oxo-,xl(g)-octalln (3) 2 1 (45 0 g 0 5 tool), 2 (36 0 g, 0 5mol) and H2SO4
(0 3 mL) tn Phil (100 mL) were refluxed for 16 h Dilution with hexane (100 mL), washing wlth
5% KC)H, drying, evaporation of the solvent and dlshllatlon gave 32 8 g or 3 (49%), 10p 112
115+C (5 ram)
R O B I N S O N - A L L A N - K O S T A N E C K I Chromone Synthesis
Synthesis of chromones or coumannes from o acyioxy aromatic ketones
HO _ OH
'C Ao NO C
A lh  AcO O [ CH,,
-CH2-- CH.oH  H,,
4 5
5 Kostaneckl S Chem Bet 1901 34 102
6 Robinson R Allan J J Chem Soc 1924 I25 2192
7 Szell Th J Chem Soc (C)Org 1987 2041
8 Hauser C R Org React 1 9 55 8 91

322 Name and Unnamed Reactions
R O B I N S O N - F O U L D $ QUmollne synthesis
Cychzation of 2 amlnostyrene denvatwes to qulnolmes
ч Cl--c--CsH,, 
2 A OCsH,,
1 2 3 H CsH,,
4
•
"CO CI Br
H
1 RObinson, R, Foulds R P J Chem Soc
1914 105 1968
2 Taylor. T W J J Chem Soc 19 3 6 181
2-n-Hexanamldostyrene (3).2 2 Ammostyrene 1 (0 5 g, 3 romol) m Me2CO (6 mL) was
treated with a few drops of conc NaOH and n hexanoyl chlonde 2 (0 6 g. 4 mmol) After 30 mln
reflux, the mixture was pOured into water and the precipitated oll solidified on standing
Recrystallization from petroleum ether gave 3 mp 6toc
2-n-Aroylqulnollne (4). 3 was heated with 8 times its welg of phosphoryl chloride for 5
mln The mixture was pOured Into water and after fdtret=on the fdtrate was made alkaline and
extracted with Et20 The plcrate of 4 roelted at t04 t05oC
R O B I N S O N - G A B R I E L Oxazole Synthesis
Oxazole synthesis from anles of (z-am.noketones
,.
1 2 (72%)
1 Rdolnson R J Chem Soc 1909 95 2167
2 GabneI. S Chem Bet 1910 43 1283
3 Wassermann. HH J Org Chem 1973 38 2407
4 Krasowtsky, BM Chem Heter Compound 1986 22 2291
2,5-Olphenyl-4-methyloxazole (2) 3 (z Benzamx'oproplophenone 1 (0 3 g. 1 1 mmol) was
added to concentrated H2SO4 (3 mL) under sllmng After 10 mln copious quantities of wter
were added until the milky white product was completely precipitated F]ftratlon and
recrystalhzatlon from petroleum ether (30-60°C) afforded 0 2 g of 2 (72%). mp B0-81°C
R O E L E N Cafoonylat=on
Cobalt catalyzed addition of CO H 2 to olehns Synthess of aldehydes
Co 1" O
23o arm H
1 2 (75%)
I Roelen O US Patent 1943 2327066
2 Roelen O
Angew Chem 1948 6O 62
3 Adkms H J Am ChemSoc 1948 70 383
4 Kropf H Angew Chem Int Ed 1966 5 648

324 Name and Unnamed Reactions
Name and Unnamed Reactiona 325
R O S E N M U N O - B R A U N Aromatic Cyanation
Cu catalyzed nucleophdic substitution of aromatic halogen by cyanide (see UIIman-Goidberg)
Br CuCN 2.5 h
A quinollnl I=- NC
Br'-" I NC --
1 Rosenmund, K.W. Chem. Ber. 1916 52 1749
2 Braun, J. LJebigsAnn. 1931 488 111
3 Newmann, M.S. J. Org. Chem. 1981 26 2525
4 Bunnett, J.F. Chem. Rev. 19 51 49 392
R O S E N M U N D Arsonylatlon
Cu catalyzed araonylation by substitution of aromatic halides See also Bart-Scheller
o-H(:X3C.C,,-Br + As(:).J  oH(:X3CC,,-A=O(OHh
3 4 S (41%)
5 Rosenmund, K.W. Chem. Bet. 1 921 54 438
8 Hamilton, C.S. J. Am. Chem. Soc. 1930 52 3284
7 Hamilton, C.S. Org. React. 19 44 2 415
o-Carboxyphenylarsonlc acid (5), 8 3 (20 0 g, 0 1 tool), AsO3K3 (50% soluhon), 4 (63
mL) and 10% KOH (63 mL) in EtOH (20 mL.) with copper powder was reltuxed at 90-95oC for 12
h, filtered hot, acidified with 20 m/HCI and evaporated. The residue was extracted with MeOH,
the solvent evaporated, the residue washed with Et20 to afford 101 g of 5 (41%) (from water).
R O S E N M U N D - S A I T Z E W Reduction to Aldehyde
Hydrogenation of acyi chioddes to aldehydes in the presence of poisoned Pd catalyst.
H p. CI. C4.CH=,O
1 2 (77%)
1 Sadzew, N. J. Prakt. Chem. 1873 114 1301
2 Rosenmund, K.W. Chem. Ber. 1918 51 555
3 Brown, H.C. J. Am. Chem. Soc. 1988 80 5372
4 Burg=haler, W. Synthesis 1978 787
5 Sonntag, A.O. Chem.Rev. 1953 52 245
S Mossettlg, E. Org. React. 1 948 4 363
p-Chlorobenzaldehyde (2). 4 To a well stirred suspension of 5% Pd on BaS04 (5 g) in
Phil (750 mL) contan#lg 2,4-dimethylpyndine (18.05 g, 0.15 mol) and equilibrated with H 2, w;.s
added 1 (43.75 g, 0.25 tool) ;n Phil (250 mL). After 1-2 h the catalyst was filtered. Evaporatio|
and recrystallization from Et20-petroleum ether gave 20.4 g of 2 (T7%). mp 45°C.
R O T H E M U N O Porphine Synthesis
Porph,ne synthesis from pyrrole and aldehydes
1 2  3 (8%)
I Rothemund, P JAm Chem. Soc 1935 57 2010
2 Undsay, J.$. Tetrahedron Left. 1986 24 4969

326 Name and Unnamed Reactiona
Name and Unnamed Reacnona
R O Z E N Hypofluortte reagents
Acetyl hypofluonte (AcOF) and methyl hypofluonte (MeOF) as fluorinating agents of olefins and
PhIC=CH= + CH.jCF  ph.,F.CH2OCH  NaOAў
 AcOF
3 1 4 (71%)
2
Ph-CH = CH-COOEt ,=cOF +
 (Ph-CH-CHF-CO,EI) AўO"  PhCH(OAc).CHF.CO2E !
F
7 2 61%
1 Rozen, S. J. Chem. Commun. 1981 443
2 Rozen,$. J. Org. Chern. 1984 49 806
3 Rozen, S. Synthesis 1 985 565
4 Rozen,$. J. Org. Chem. 1987 52 2588
5 Rozen,$. J. Am. Chem. Soc. 1991 II3 2648
6 Rozen,$. AcChem. Soc. 1988 2I 307
Methyl hypofluorlte (1).5 A flow of 10% F 2 in Ar was passed at a rate of 100 mtJmln into 2.5
tnL MeOH and 2.5 mL EtCN at -78oc. After I h a 2N (5 retool) solution Of 1 was obtained.
1,1"Olphenyl-l-fluoro-2omethoxyethane (4).5 1,1-Diphenylethene 3 (250 rag, 1.4
mmol) in CH2CI 2 (5 mL) was treated with 1 (4.5 retoOl) in MeCN (70 mL) at -40oc. After 40 rain the
mixture was poured into water, extracted with CH2CI 2 and the solvent evaporated Chroma-
tography of the residue (sdioa gel Merck EtOAc/petroleum ether) afforded 221 mg of 4 (71%).
l"Methoxy-2-fluoronapltthalene (8).2 To 7 (3.16 g, 20 retool) in CH2CI2-CFCI3 was
added a solution (-75oc) of 2 (excess of 10-50%). The reaction was quenched wdh 500 rrd.
water after 80-90% conversion, the organic layer washed with aq NaHCO3 and the solvent
evaporated. Chromatography afforded 2.16 g of 8 (61%) and 0 28 g of 9 (8%).
RUFF - FENTON Degradation
Oxidative degradation of aldoses via z-hydroxy ecls to lower chain aldoses.
CHO CO2Ca
I I
HCOH Br2 HCOH Fe2(SO4s, H20 =
 H--COH
I co I eo I
HmCOH
CH=OH
CH=OH CHOH
1 Ruff, O. Chem. Ber. 1 898 3I 1573
2 Fenton, O Proc. Chem. Soc 1 8 9 3 9 113
3 Fletcher, H.G. J Am. Chem. Soc 1 950 72 4546
D-AXablnose (2).3 A medure of calcium gluconate =hydrate 1 (200 g, 0.43 tool) (obtained by
Oxidation of D-glucose), Ba(OAc)2 (20 g, 0.08 mot) and Fe2(SO4) 3 (10 g, 0.025 mol) was stirred
in water (2000 mL) until a precitate appeared. The susponslon was filtered and the brown
Solution was treated wdh 30% H202 ( 129 mL) at 35°C A second portion of 30% H202 ( 120 mL)
was added and the temperature was raised to 40"C After filtration on Norrite and concentration
under vacuum, MeOH was added and the precipitate filtered and recrystallized to give 55-60 g
Of 2 (50%), mp 162-164oc, [z]2[, + 103 °.

328 Name and Unnamed Reactio
Name and Unnamed Reactions
R U P E Rearrangement
IsOmedsation of ethynyl carbinols o unsaturated cad:nyl compnds.
OH
1
2 (49%)
3 (08%)
1 Rupo, H. He/v. Ch/m Acta. 1920 9 672
2 Rupo, H. Helv. ChmAct 1938 I7 238
3 Chentey, J.O. J. Am. Chem. Soc. 1948 70 246
l"Acetyl-l-cyclohexene (2) and Cyclohexylldeneacetaldehyde (3). A mixture of 1-
ethyrlyl"1-Chexanol 1 (65.0 g, 0.5 tool) and 90% HCOOH (400 mL) was refluxed for 45 rain
The cooled mixture was poured into water (2000 mL) and extracted wth petroleum ether. The
organic layer was washed with 10% NaOH, the solvent evaporated and the residue was carefully
fractionated. Ore obta,ns 32 g of 2 (49%), 10p 111°C (49 ram), n. 1.5020, semicaazone,
mp 188-192C.
RUZICKA . FUKUSHIMA Rearrangement
Base or acid catalyzed rearrangement of 17-hydroxy-20-keto steroids to D-homo steroidS.
O ]-OH HO CH
1 Ruzicka, L Helv. Chm. Acta 1 9 3 8 21 1760
2 Fukushlma, D K. J. Am. Chem. Soc. 1 955 77 6585
3 Wendler, N.L. J. Am. Chem. Soc. 1956 78 5027
3'17a-Olhydroxy-17a-methyI-O.homoandrostane.17.one (2).2 A solution of
3-acetoxy-17-hydroxyaliopregnane-20-one 1 (250 ml.., 0 68 mmol) In EtOH (200 mL) and
10% KOH (200 mL) was refluxed for 4 h. The cooled alkahne solution was extracted wdh
EtC)Ac, the organic layer washed with bdne and the solvent removed in vacuo
Chromatography of 223 mg of crude product on silica gel (80 g) and eluton with CH2CI 2 EtOH
affol'ded 150 mg of 2 (60"/.) Recrystallizaton from Me2CO gave 120 mg of 2, mp 199-200°C,
[(x]206 - -36 5 °.

330 Name and Unnamed Reactions Name and Unnamed Reactiona 331
S A K U R A I Nlylaton
"1"] mediated kter or intramolecular addition of allylic sdanes o (z,lunsaturated ketones or to
aldehydes.
I Sakural, H
2 Wilson, S.R.
3 Schnltzer, H.
4 SakuraL H.
5 Sakural, H
6 Seebach, D
7 Sakural, H
J Am. Chem Soc. 1977 99 1673
JAm Chem. Sc. 1982 I04 1124
Synthesis 1 98 8 263
Tetrahedron Left. 1 976 1295
J Org. Chem 1984 49 2808
Angew Chem Int. Ed. 1985 24 765
PureAppl Chem 1982 54 1
9-Allyl-2-decalone (3)oi To , 1.9 2-octalone I (300 mg, 2 retool) and TICI4 (380 mg,
2mmol) m CH2CI 2 (5 mL) at -78°C was added a solution of tnmethyl allyl silane 2 (t59 mg, 2 8
retool) n CH2CI 2 (3 mL); the reactk)n is exolhermў After stlmng at -78oc for 18 h and at -30'C
for 5 h. hydrolysis, extraction and distdlaton gave 353 mg of 3 (85%), bp 120oc (5 mm)
Phenylallylcarblnol Isopropyl ether (6). 8 Benzaldehyde 4 (106 mg, 1 retool) was
treated with dilsopropoxydichlorotltanlum 5 (225 mg, I I mmol) at .75oC and subsequently 2
(136 8 rag, I 2 mmol) was added Work up led Io isolation of 171 mg of 6 (90%)
S A N O M E Y E R Isatln synthesis
balm synthesis from anilines.
1 Sandmeyer, T. Helv Chm. Aca. 1 91 9 2 234
2 Shellley, F.E. J. Org Chem. 1958 21 171
4,5-Olchlorolsatln (4). 2 A suspension of 1 (10 0 g, 66 retool) in water (50 mL) and 35% HCI
(12 mL) was treated wdh Na2SO4 (66 g), chloral hydrate (10.5 g, 63 mmol) in water (224 mL) and
hydroxylamlne hydrochiodde (13 0 g, 187 mmol) in water (60 mL), and stirred at I00"C for 150
rain. The mixture was kept 24 h at 20°C, the solid was filtered and dissolved in I% NaOH (750
mL). The insoluble 3 was removed and the solution was acidified with 35% HCI (25 mL) to afford
10.8 g of 2 (75%), mp 190-191°C: after recrystallization from Phil or EKH-H20, mp 197"Co
To preheated 98% H2SO4 (70 mL) under sttrdng was added 2 (20.2 g, 87 minor) dudng 30 rain.
The mixture was heated to 105°C for 10 rain. and then allowed to cool to 30°C and poured into
Cold water (400 mL). The precipitate was collected, washed and dned to yield 16 5 g of 4
(98 8%), mp 253-254°C, from EtOH, mp 260 5-26t°C

332 Name and Unnamed Reactions Name and Unnamed Reactiona 333
SANDMEYER . GATTERMANN Ammattcsobstitutlon
Substdution of an amine group via the dlazonluro salt by nudeophiles such as CI', Br', I', CN-,
R-S', HO-, some wa cuprous salt catalysis.
1
CaHsNH NOz a"
1 Sandmeyer, T .Chem. Bet.
2 Cattermann, L. Chero. Bet.
3 Hn, H.H. J. Che 
4 , N. J. Chero.  Pn T
5 Hn, H.H. . Rev.
6 edl, E. . Ch.
2 (%)
HI
7 CsHs'I
4 (100%)
1884 I7 1633
1890 23 1218
1944 22
1987 645
1947 40 251
1983 65 155
p-Nltrochlorobenzene (2). A hot solution of IPnitroanlllne 1 (2.6 g, 19 mmol) in 32% HCI
(50 mL) was cooled and treated with NaNO2 (2.0 g, 29 retool). After 30 mn of stirring Cu2CI 2
(2.0 g) and CuCI 2 H 20 (3.4 g) was added. The rnedura was lolled ior 30 mln and steam
dstilled. Frooro the distillate by extraction them are obtained 3-3.05 g of 2 (94-96%), mp 63-
84°C.
Iodobenzene (4). Aniline 3 (9.1 g, 0.1 tool) and 5P/o HI solution (0.3 mol) was diazotized by
addition of NaNO2 (6.9 g, 0.1 mol) In polyethylene glycol 200 (PEG 200, 2.0 g) and CH2CI 2 at
0"C. There are obtatned 20.4 g of 4 (100%)
S A R E T T Oxidizing reagent
Oxidlzatlon of an alcohol to an adehyde or ketone with CrO3-pyddlne.
1 2 189%1
1 Sarett, L.H. J Am. Chem. Soc. 1 953 75 422
2 Holum, JR. J. Org. Chero. 1961 26 4814
3 Gassmann, P.G. J. Org. Chem. 1 964 28 323
4b-Methyl-7-et hylenedloxy. 1,2,3,4,4a,4b,S,6,7,8,10,10a.dodeca h yd ro-
phenanthrene-l,4-dlone (2). I A solution of 4b-roethyl-7-ethylenedloxy.
1,2,3o4o4ack4b,5,6, 7,8,10,10a,dodecahydrophenanthrens-4-Ol-l--one 1 (3.12 g. 10 mmol)
in pyddine (30 mL) was treated wth 3.1 g of CrO3 m 30 mL of pyddioe. The reaction mixture was
maintained for 24 h at 20°C, poured into water, extracted three times with PhH.Et20 (1:1),
filtered through Supergel and the solvent evaporated The residue, after recrystallization froro
Et20 gave 2.76 g of 2 (89%), mp 117-120°C.
Reagent. The yellow CrO3-pyndine reagent is prepared by adding red CrO3 at 15-20 ° to 10
parts of pyddlne in portions wdh st,mng. The complex IS moderately soluble tn pyridine and
Used as a suspanson to which a 10% solution of the alcohol in pyddioe is added Note: if
pyndine is added to CrO3 the rnudure usually inflamed

334 Name and Unnamed Reactions Name and Unnamed Reaction. 335
S C H M I D T Rearrangement
The use of HN 3 in the conversion of carboxylic acx:ls to amides, of aldehydes into intnies, or of
ketones into tetrazoles or amides (wth retention).
O N- H 0
1 2 (4%)
R, yN,CO=E .... C NOH=I'
R1 OEt 7 O R H (80-99%)
I Schmidt, K.F. Z Angew. Chem.
1923 36 511
Tetrahedron 1970 26 4329
2 Greco, C.V.
3 Bach, R.D. J. Org. Chem.
1982 47 239
4 Parlor, PA. Chem. Heter. Compd. 19 86 22 140
5 Hassner, A. J. Org. Chem. 1988 53 22
6 Applequist, D.E. Chem. Rev.
1984 54 1084
7 Wolff, H. Org. ReacL 1984 3 307
Lactam (2).2 Cooled 9-methyl-&5,10.octalln.l,6.dion e 1 (2 g, 11.2 mmol) in 98% H2SO 4
(40 mL) was treated with NaN 3 (I 46 g, 22.4 mmol) at 5°C for 45 rain, stirred for another 60 rain
at 5°C, and poured OntO ice (200 g). Extraction wdh CH2CI2, washing (5% KOH, water) dPpng
(MgSO4) and evaporation afforded 1.7 g of 2 (74%), mp 221-231,C. Rec;'ystallization
(EtOAc) gave 1 g of 2 (46%), mp 234-236oc
S C H M I T Z Diazlndlne Synthesis
Dzindme synthesis from chioramlne, ammonia and (excess) aldehyde In the presence of
excess aldehyde formation of blcyciic tnazolldines takes place
3 187%)
1 Schmltz, E. Angew Chem. 1959 71 127
2 Schmltz, E. Chem. Ber. 1962 95 680
3 NIISen, A.T. J Org. Chem. 1976 41 3221
4 Schmltz, E. Chem. Bet. 1 967 100 142
tie (trane)-2,4,f-tri-(n-pentyf)-l,3,5-trlazabfcyclo[3.1.0]hexane (3).3 A solution of
t-butyl hypochionte (2 71 g, 26 mmol) in t-BuOH (3 mL) was added at -35'C over 5 mm to a stirred
10 N methanollc ammonia solution (25 mL), foliowed by hexanai 1 (5.0 g, 50 mmol). The rr, xture
was stirred for 2.5 h at 20'C, the solvent was removed n vacuum and the residue was extracted
Wth bo,ing hexane to afford 4.25 g (87%) of a mixture of cS and trans 3 in a ratio of 3.3 6 7 (exo).
The less soluble fraction from hexane gave 0 67 g of 3 trans-exo (13%), mp 51-52°C, 3 ClS-exo,
rnp 50.540C

336 Name and Unnamed Reacnons Name ad Unnamed Reacnons 337
S C H O L L Polyaromatiў synthesis
Preparation of ondensed polynudear aromatics by Fdedel-Crafts catalysts
1 2 (86%)
I SchofI. R. Chem.Ber 1910 43 2201
2 Scholl. R. Monatsh. 1912 33
3 Nenltzescu. CD. Chem. Bet 1958 91 2109
4 Vlnglello, F A. J Oq/. Chem
1971 36 2053
5 Allen, C.FH. Chem Rev. 1959 59 987
DIbnzo-(a.1)-pyrene (2).4 To a refluxlng rrdxture of AICI 3 (0.6 g, 4 5 retool) and SnCf 4 (0
g. I 9 retool) In Phil (25 mL), was added a hot soMion of 1-phenyt-benz(a)antracene I (30 rag,
0 1 retool) In Phil (25 mL). After 5 h reflux the rndure was poured into 10% HCI (500 mL), the
oganic layer was separated and the solvent evaporated In vacuum. To the residue was added
95% EIOH (5 mL) to oMain 0 2 g of 2 (66%), mp 160.163oc, Jstaized from PhH'EIOH, mp
182-163oC
S C H ( L L K O P F Amino acid synlhesis
Asymmeldc synlhesis of amino acids from dlhydropyrazlnes
O
Pr . MeO Me
iPr',.,_N  ,.OMe t n8ub  ,,,=N..,.,.OMe
MO • 3 t8u SK N 2 N
X2
3 X = Br 5 (72%). 95% ee
4 X = S 18u (93/.)
t Sch611kopf. U Synthess 1 9 81 969
2 Sch611kopf, U Llebg's Ann 1S 82 1925
3 Sch611kopf, U Synthesis 1 9 8 3 3 7
4 Schlkopf, U Synthesis 1 S85 1052
(3S,6R) pyrazlne (4). 3 To 1 (2 77 g, 14 mmol) In THF (25 mL) al 70°C was added 1 8N BuL,
In hexane (8 3 mL, 15 mn'l) followed after 15 rain by CH2Br 2 (26 1 g, 0 15 moo In THF (15 mL)
After stlrdng 30 h at -70°C, work up affon:led 3 2 g of 3 (79%), bp 760-60"C (0 1 Ion')
To IJoutylmemaptan (0 32 g, 3 5 mmol) in DMSO (10 mL), was added KOtBu (0 37 g, 3 3 mmol)
and after 5 rnln a solulion of 3 (0 87 g, 3 mmol) n DMSO (2 mL) Sllmng was continued for 5 h at
70C and the solulon was mixed wllh elher (30 mL) and shaken with water (10 mL) After drng
and dlslillallon 0 837 g of 4 (93%), bp 80 90°C (0 1 Ion') was Isolaled
(R)-S-t-Butyf-a-methylcystein methyl ester (5). 3 A suspension of 4 (0 75 g, 2 5 mmol)
In0 25 N HCI (20 mL) was Slln'ed at 20oc for 5 clays, washed with EI20 ar'd evaporated The
residue (5 HCI and VaiOCH3 HCI) was dissolved in water, EI20 was added, followed by amrrnla
(Io pH=8-10) wdh shaking The EI20 exlract was dlsldled (VatOCH3 forerun) Io afford 0 37 g of
5 (72%), bp 60-70°C (0 1 loft), [])0 = 16 3 ° (c 1 0 EIOH), e e >95%

338 Name and Unnamed Reactwns Name and Unnamed Reacnons 339
S C H 0 L T Z IndollZlne synthesis
Indollzine synthesis from reaction of pyndlnyl ketones wdh aldehydes In Ihe presence of
ammonium acetate
0 (. =CH-A
1 2 N-CH-CsH4- Cl
N=CHAr 
3 (39%)
I Scholtz, M Chem Bet 1 912 45 734
2 BarOw, ET Chem. Ber 1948 42 838
3 Kmhnke, F Chem Ber 1971 I04 1624
4 Uchida, T Synthests 19 7 8 209
l"(4"Chlorobenzylldonoamlno)-3-(4-chlorophenyl).lndollzine (:3) 4 A mmture ol 2
acetylpyddlne I (2 4 g, 20 mmol), p-chlombenzaldehyde 2 (5 6 g, 40 mmol) and amrnomum
acetate (20 g, 0 33 mol) in AcOH (30 mL) was heated for 30 mm under stirring on a water bath
To the modure MeOH (20 mL) was added and stimng was contlned for another 15 rain at Ihe
same lemperature After 24 h the product was filtered and chromatographed on alumina
(neutral actlvdy 1. eluent CHCI3) There are obtained 2 9 g of 3 (39%), mp 167-168oc
S C H W A R T Z Hydrozlrconation
Hydmmrconatn with CP2Zr(CI)H and Mmhael addibon of the Zr reagent
1 NiAcac
4 (S1%)
WalleS, CP J Organomelal Chem 1970 24 405
Schwartz, J JAm ChemSoc 1974 96 8115
Schwartz, J JAm Chem Soc 1980 102 1333
Schwartz, J Angew Chem Int Ed 1976 I5 333
Naglshi. Ei Ichi AMnchlmicaActa 1985 I8 31
Schwartz, J Ch;mca Scnpta 1989 29 411
$'(1-Octen-l-yi)cycfopentanone (4) 3 Chlorobls (T s cyclopentadlenyl)
hydndozlrconJm 1 (38 68 g. 0 15 tool) in THF (50 mL) under Ar was Ireated with 1-ocb/ne 2
(23 6 mL. 0 16 tool) at 15 25°C After 18 h stlmng at 20°C. 2-cyciopentenone 3 (10 9 mL. 0 13
tool) was added and the modure was kept for 10 min In an ice bath Nickel acetylacetonde (3 34
g. 13 mrnol) was added in three portions at 10 rain intelvais below 40°C After 2 h sttmng at 5°C
and 2 h at 20oc the rrflxture was quenched with 1 N HCI (150 ml_) and ice water (200 mL)
Extraction with hexane washing and evaporation of Ihe solvent, afforded 24 79 g of crude
product Chromatography on silica gel (2% EIOAc in hexane and 4% EtOAc In hexane) gave
15 43 g ol 4 (61 2%)

340 Name and Unnamed Reacttona Name and Unnamed Reacnona 341
S C H W E f Z E R Allylamlne synthesis
Synthesis of E allylamlnes from vlnylphosphon,um salts and aldehydes (wa W'lg react=on)
Br OH.'-V nBu, P I
n Bu. P°"'
2 3
O O
)hCHO + HN  "'Ph  Ph ..,..,,,,,.NH
3
O
4 $ 6 (80%) 7 (83%)
1 Schwelzer, EE J Org Chem 1966 31 467
2 Rouhut MM J Org Chem 1963 28 2565
3 Evans, D A J Am Chem Soc 1978 100 1548
4 Meyers AI J Org Chem 1981 46 3119
(E)-3-Phenylpropenylamfne (7). 4 n Bu3P 1 (131 g 0 65 mol), 1,2 dlmethoxyethane
(DME) (300 mL) and 2 (72 2 g. 0 68 mol) were relluxed for 4 h 48% HSr (1 mL) and ,sopentyl
acetate (243 mL 2 2 mol) were added and reflux continued for 3 d After evaporallon
residue was Ireated with DME (400 mL) and Na2SO3 (68 9 g 0 65 mol) and refluxed for 48 h
Filtration evaporation and trealment with EIOAc gave 100 g of 3 (57%), mp 149 5 150 5°C
Nail (1 5 mmol) was washed (pentane) treated In THF wth 4 (0 3 g, 1 retool) 3 (0 4 g, 1 3
retool) and phthal,mlde 5 (0 19 g, 1 3 mmol) and healed at 60°C (TLC CHCI 3 EI20 hexane
5 1 4) Trealment wdh 5% cltnc acid in water and extraction wlth EI20 gave 281 mg of 8 (80%)
mp 150 151"C
To 8 (174 rng, 0 6 tool) in anh EIOH (19 mL) was added 95% hydmzlne (60 mL 1 8 retool) 4
h reflux aciddlcaton Io pH=2 heahng for 1 h, filtration dilution of Ihe filtmle extrachon with
EI20 and baslfication gave 93 mg of 7 (83%) mp 101 102°C 100% E
S C H W E I Z E R Rearrangement
Thermal react=on of "allenyl azlnes" denved from propargylphosphomum salts with ketenes,
socyanatas, CS2 or phthalic anhydnde to form b and Incycllc lused pyrazolo heterocycles
.NH2 Ph
Ph--C-CO2Me =, N
1 2 Mel 3 NaOMe 
CH , + 2
3 p ph 3
N "" NH= 3/Ar-N-C,,O
II
Ph--C-C-Ph
1 Schweizer E E J Org Chem 1 g 7 8 43 4328
2 Schwelzer E E J Org Chem 1 9 8 7 52 1810
3 Schwelzer EE J Org Chem 1990 55 1687
4 Schwelzer, EE J Org Chem 1990 55 6363
6,7-Oimet hyl- 3-met hoxy-3-phenyi- 1 .(2,6.dimet hylphenyl)- 1 H-imidazo(1,2-b)
pyrrazol-2(3H)-one (3)2 Phosphorane 2 (t 48 g 3 mmol) and 2 6 dlmethylphenyhsocya-
hate 3 (0 59 g 4 mmol) ,n PhMe (30 mL) was heated under reflux with stlmng for 16 h (TLC
EtOAc hexane 1 6) Evaporation and column chromatography (silica gel EtOAc/hexane 1 6)
afforded crude 4 Recrystalhzation from Et20 petroleum ether gave 0 930 g (86%) mp 128 5
130oc

342 Name and Unnamed Reacnon.ў Name and Unnamed Reatnon.ў 343
SEMMLER - WOLFF - SCHROETER Ox,'nsAromattzatlon
Aromatization of cyciohexanone oximes to anilines
O
,,
HO-N CH CH=--C-NH 
reg 18 h 
H 2 ('/.)
I Semmler, w Chem Bet 18 9 2 25 3352
2 Wolff, L Lebgs Ann 1902 322 351
3 Schroetter, G Chem Bet 1930 63 1308
4 Cook, JM J Org Chem 1980 ,5 2585
S I M O N I S Benzopyroge synthesis
Benzoc)ymne synthesis from phenols and  ketoesters
EtO2C CH. lOO" 2h v  -CHj
1 2 3 (tO"/,
I Simonls H Bet 1913 46 2014
2 Slmonis H Bet 1914 47 2229
3 Lacey RN J Chem Soc 1954 654
4 Sethna S M Chem Rev 19 45 36 14
5 Sethna, S M Org React 19 53 7 15
S H A R P L E S S Asymmetnc Epoxidation
Enantoselective epoxidabon of allyl alcohols by means of t,'tanlum alkoxx::le. (+) or ( ) diethyl
tartarate (DET) and t butyl hydroperoxlde (TBHP)
1 2 ("/7%) 9S% ee
r(Pr), i.. H OH + OHH
ethro 98 2 Ihreo
1 Sharpless, K B
2 Sharpless, K B
2 Sharpless K B
4 Sharpless, K B
J Am Chem Soc 1980 102 5974
J Am. Chem Soc. 1981 I03 464, 6237
J Am Chem Soc 1987 I09 5765
Aldnchmca Acta 1 9 8 3 16 67
2(S),3(S)-Epoxygeranioi (2) 1 To CH2CI 2 (200 mL) at -23°C was added sequent=ally
under st,rnng tltantum tetratsopropoxxe (5 68 g. 5 94 mL 20 retool), L(+)DET (4 12 g 3 43
mL 20 mmol) and after 5 mn geranlol 1 (3 08 g. 3 47 mL, 20 mmol) and 3 67 M of (TBHP) 40
mmol n CH2CI 2 After 18 h at 20°C 10% aqueous tartanc acid (5O mL) was added under
stlmng and after 30 mn the mixture was healed to 20'C and s|lrred for 1 h The organic layer
was washed, dned and evaporated The o,ly resxtue was diluted with E|20 (150 mL) washed
with 1 N NaOH (60 mL), bnne, dried and the solvent evaporated Chromatography on s,lica
gel affon::led 2 6 g of 2 (77%) 95% ee [(J204 - 8 36'C (c I 5, CHCI3)

344 Name and Unnamed Reactions Name and Unnamed Reactions 345
S H A R P L E S S Asymmetric Dlhydmxylation
Enntioselective syn dihymxylatlon of olefins using AO-ml formed from phthalazlne-
dihydroquinidine 1 or AD-ml-0 formed from phthalazine-d,hydroquinine 2 and OsO4.
1 (OHQO k- PHAL 2 ( (DHQ k . PHAL
Ph Ph. H
AD-mix (z H- -'/ - -Ph
 0o C =
OH
3 Ph HO4 (S,S) (.06%, 99%ee)
1 Sharpless, K.B. J An Chem. Soc 1 988 110 1968
2 Sharpless, K.B. Tetrahedron Lett. 1 990 31 2999, 3817
3 Sharpless, K B. J. Org. Chem. 1 992 57 2768
4 Soderquist, J.A. J Org. Chem 1 9 9 2 57 5844
5 Sharplass, K B. Org Synth. 1 9 91 O 47
AO-mlx (o. or {).1 A mixture of K2OsO2(OH)4 (0 52 g) and (DHQ)2-PHAL 2
(dihydroqulnine-phthalazlne) or (DHQD)2-PHAL 1 (dlhydroqunK:hne-phthalazine) (5.52 g)
was mixed wdh powdered K3Fe(CN)s (700 g) and K2CO3 (294 g). The mxlure was kept
dry, ready for use in the next step 1,2-Olphenylethanediol (4) (S,S) or (R,R). AD-
rrex (o.) or AD-mx ) (1 4 g) was stilted at 20°C into t-BuOH (5 mL) and water (5 mL).
Methanesulfonamlde (95 rag, lmmol) was added and the mixture was cooled to O°C. Under
vigorous stlrr,ng, trans stllbene 3 (18O rng, lmmol) was added (mondored by tic or gc).
Na2SO3 (1 5 g) was added and after 1 h the mixture was extracted with EtOAc. Washing (2N
KOH) and flash chromatography (s,lica gel EtOAc-hexane) afforded 205 4 mg of 4 (96%),
99%ee, [czj24D - +90.0 o or -90 0 ° (c 1.2 EtOH).
S H E R A 0 S K Y Rearrangement
Rearrangement of O-(2-pyddy)oxlmes to 2-pyndones via a hetem-Cope rearrangement.
2 1
1 Sheradsk, T. TetrahedronLett 1966 5225
2 Sheredslej, T. IsraelJ. Chem. 1968 6 659
3 Sheradsky, T. J. Org. Chem. . 1 9 71 36 1061
4 Lamnze, J.Y. Terahedron LetL 1989 30 2229
0,,(2-Pyrldyl)oxlme Of 1-tetralone (3). 3 1-Tetraione oxime 1 (3.22 g, 20 mmol) and t-
BuOK (2.2 g, 20 mmoi) in dry DMSO (40 mL) was stirred under N2 for 30 min and 2 (1 94 g, 20 "
retool) in DMSO (40 mL) was added. Stzrring was continued for I h at 20°C and 3 h at 90°C. The
solution was poured into water (3O0 mL) and the preczpltate clystagized from MeOH to afford
2.38 g of 3 (50%), mp 224°C.
3-(1-Oxo,.2.tetralyl).2-pyrldone (4). A solution of 3 (1.0 g, 4 1 mmol) in ethylene glycol
(20 mL) was refluxed for 20 h under N 2, and poured into water (1 O0 mL). The preclptate was
cP/'stalkzed from EtOH to yield 0 73 g of 4 (73%), mp 206.207°C.

Name and Unnamed Reacion Name and Unnamed Reaction 347
S H E S T A K O V Hydrazine synthesis
Synthesis of (x-hydrazino zdcfs from a-amino aads via ureas.
Me
NCO CO
OMe o  NH
1 2 (7S%) 3 (48%)
1 Shestakov, p. Z. Angew. Chem. 1903 I6 1061
2 Karady, S. JoOrg. Chem. 1971 36 1949
3 Viret, J. Tetrahedron 1987 43 891
4 Kost, A.N. Russ Chem. Rev 1964 33 159
L'c'(3'4"Olmeth°xybenzyl)'c'hydrazlnoproplonlc acid (3) 2 L-o-Amlno-o-(3,4-
dimethoxybenzyl)pmpionlc ac,:l hydroclllodde 1 (44 0 g, 0 | 6 tool) in water (440 mL) was
Veated at 5"C with KCNO (77.6 g, 0.96 tool) in sinai polltons. The aurry was heated at 60°C for4
h and then filtered. The filtrate was acidified with 35% HCI to pH 1,. The product was flgered,
washed and dried at 50oc, to give 34 5 g of 2 (74"6%), mp 205-207C.
To ice-cooled 2 (2.2 g, 7.8 mmol) in 2.5 N KOH (15.6 mL) was added 0.17 N NaOCI (13 7
9 75 mrri). The solution was heated to 80°C for 1 h, PhMe (45 mL) and hydraztne hydrate (0 8
mL) was added followed by 6 mL of 35% HCf, wh,la the mixture was sted vigorously. After 30
min stirring at 80oc, the aqueous layer was extracted, the extract was evaporated to dryness and
the residue digested with EtOH. The EtOH solution was treated with Et2NH to pH 6 4 and the
product filtered, washed, and dried to give 1 g of 3 (48%), mp 222.224oc, [czjD = .9 o (H20)
S I E G R I S T St,bane Synthesis
Synlhesis of sblbenes by base catalyzed condensation of reactive toIuenes with
benzatanilines.
CH 3 + PhN. CH-Ph  Ph
1 2 3 (94"/,)
t Siegrist, A.E. I-lelv Chlm Acfa. 1 967 50 906
2 Siegrist, A.E. I-lelvChmtAcfa. 1969 52 1282
3 Newrnan, M.S. J. Org. Chem. 1978 ,3 524
:Z-(Slllban-4-yl)benzo(b)furan (3).2 A mixture of 2-{p-tolyl)benzo(b)furan 1 (2.6 g, 12.5
retool), benzalandtne 2 (2.27 g, 12 5 mni) and powdered KOH (6 25 g, 0.1 mol) in DMF (100
mL) was sttwed and heated to 90"C for 30 rain and to 90-95.C for another 60 min. To the cooled
mixture was added water (100 mL) and 10% HCI. The product was filtered, washed with water
and MeOH, to give after dry,'tg 3 5 g of 3 (94%), mp 270-271°C.

348 Name and Unnamed Reactions
SIMMONS . SMITH Cyclopropanatlon
Cydowopana fomlatlon from alkenes with alo/idiiodldes and Zn-Cu (cadoenoid addition to
double bonds).
1 2 (46"/.)
o,SMe
CHI
1 Simmons. H.E.,Smith, R.,D J. Am. Chem. Soc. 1958 80 5323
2 Koch, so. J. Org. Chem. 1961 26 3122
3 Girard, M.
Syntllests 1 9 7 2 542
4 Denise, J.M.
Synmes4s 1978 550
5 Mod, A. Tetrahedron 1986 42 6447
6 Simmons. H.E. Org. React. 1973 20 1
Zinc-copper couple. Zn dust (120 g. 1.85 at) and CuO (15 g, 0.18 reel) were heated
carefu in a stream of H 2 at 425-450oC for 90-100 rain, heated for an additional 4 h at the
same temperature and cooled under H 2
cle and trans Trlcyclo [7,1,0,0,4,$] decane (2). 2 The Zn-Cu couple (10 g) covered
with Et20 (70 mL) was treated with a few drops of CH212 to start the reaction. A mL'dure ofl
(10 8 g, 0.1 mol) and CH212 (145 g, 0.54 mol) in EI20 (300 mL) was added dropwise dunng 20
rain under stimng and a II was refluxed for 36 h. Zn-Cu and CH212 were removed by washing
with Na2S203, and distillation gave 6 5 g of 2 (48%), mp 38-39oC, bp 42.43C (3 5 111111).
S K A T T E B g L Dhalocyciopropane Rearrangement
Rearrangement of gem-dihalocyclopropanes to allenes or of vlnyt dthafocyopropanes to
ўycJopentadienes and fulvenes by Me
....
so% NaH MILJ
/ 2 (5P/o) 3 (87%)
 8r
4 (8o%) 8 (49%)
1 Skatteb)i,L. Tetrahedron 1967 23 1107
2 Skattebl, L. Te,ahedron Lett. 19 77 2347
3 Skattebbi, L.
Acta Chem. Scand, B 1984 38 783
4 Paquette, L.A. J. Org Chem. 1987 52 4732
5 Skatteb)l,L. J.Org Chem. 1964 29 2951
6 Skattebl,L AcaChem. Scand.,B 1984 39 549
Oibmfflocyclopropane (2). 4 To a suspension of 1 (29 6 g, 0.42 moi), CHBr 3 (26.2 mL,
0 3 reel), triethylbenzylammonum chfonde (TEBA), I 09 g, 4.4 mmol) and EtOH (0.8 mr.) in
CH2Ct2 cooled in an ice bath, 50% NaOH (100 mL) was added dropwtse dudng 10 rain. The
mixture was stirred for 24 h at 20"C and poured into water (250 mL). Wed(up afforded 32.5
of 2 (55%), bp 85-95°C/0 06 Ton'.
(1R)-(-)-9,9-Olmethyitricyclo (6.1.1.02.S)deca.2,5.dlene (3).4 2 (17.6 g, 55
retool) in dry Et20 (2000 mL) at 0 ° was treated wdh 1 5 M MeLJ in EI20 (220 mmol), stined for
10 h at 20oc and quenched with ice water (1000 mL) Wokup, passing through neutral
aUmma and bulb to bulb distillation ) afforded 7 7 g o! 3 (SP&), bp 90,/5 Ton', [oJ203 - -21
(c 1 76, EIOH).

350 Name and Unnamed Reactions
Name and Unnamed Reacnon
S K R A U P Quinoline synthesis
Qulnoline synthesis from anilines and acroleln or glycerol
 H
C1.%O  +
NH=
NO2
1 2
3
"" . p-;:--p ---..
OH OH OH
4
1 Skrp, Z H. Chem. Ben 1880 13 2086
2 Yale, HL J.Chem.. 1948 70 254
3 Wahmn, M. Tetrahedmn
194 20 2773
4 Bertmm, Chem Rev. 144 35 152
5 Mane, R H.F. O.Re. 153 7 59
6"Methoxy-8-nltroqulnollne (3).2 A mixture of 3-nltro-4-amlnoanisote 1 (33 6 g, 0 2 tool),
arsenic acid (58 8 g, 0.4 mol) in 85% H3PO 4 was healed Io 100oc and acmleln 2 (15 94 g,
0 284 tool) was added dropw,sa under stlmng. After all of 2 was added (25-30 re,n), Ihe mixture
was maintained for an additional 30 n',n a! Ihe same lemperalure. The solution was poured inlo
waler (800 mL), decoionzed with charcoal and made alkaline with NH4OH The precc)ltale afler
flitralion and recryslalllzation from EIOAc (600 mL) gave 25 g of 3 (6O%), mp 157-158°C
s M I L E S Aromatic rearrangement
Rearrangement by nucleoph,lic aromatic substitution and aromatic migration from one hereto
atom to another (O to N or S to O)
o" v H- o . ON  H )
1 2 (%)
o x
o
1 smls, s. J. Chem S 1931 2364
2 Giln, N.V. J  Chem.
1973 38 373
3 Bayles, R. Synthes;s 19 7 7 31
4 8unnet, J. Chem Rev 1 951 49 362
5 Husgen, R Angew Chem. 19 6 0 72 314
6 Trace, W E. O ReacL 1970 18 100
N'(p'Nitrophenyi2-hydroxyacetamide (2).3 A solution of pnltmphexyacetame
1 (2 7 g, 13 1) In DMF (20 ) was treat wdh a 5O% snsmn of Nail (0  g) T
xm was stiffed for 1 h  5C, water was a a the  mcwstaliized from EtO
to afford 1 2 g of 2 (45%),  1C

352 Name and Unnamed Reaction Name and Unnamed Reaction 353
SMITH . MIDOLETON . RQZEN Fluonnation
Conversion of carbonyls to CF 2 compounds by SF 4 (Smith) or dlelhylamnosulfur thfluonde
(DAST) (Middleton) or by IF on hydrazones (Rozen)
(ч) -.-co + SF,  (+)F-?H.C
Et 9d
Et (,%)
._o NzH4 -- N'NH2 IF F F
1 Berg, MA. BulI. Soc. Chm Fr 1925 37 637
2 Smlth, W.C. J. AITLChem. Soc. 1959 81 3165
3 Rozen. S. JAm. Chem. Soc 1987 109 896
4 Middleton, W.J. J. Org. Chem.
1975 40 574
5 Boswefl. G.A. O. React. 19 7 4 21 1
Iodine fluoride (IF). A suspension of well-ground ,:)dine (25 g), in CFCI 3 (500 mL) was
sonicated for 30 rnln. cooled to -78'C and agitated with a vibromlxer Nitrogen-diluted F 2 (10%
v/v) was bubbled through (1 1 equiv ) to give ; light brown suspension of IF.
4-tert-butyf-l,l-dlfluorocyciohexane (4).3 Ketone 1 (5 g, 33 mmol) ,n EtOH (15 mL)
was added to hydrazne hydrate 2 (10 g) in EtOH (40 mL) and heated to reflux, then diluted wth
water, extracted with CHCi3, dried (MgSO4) and the Solvent evaporated to give 5 5 g of 3
(100%). A solution of 3 (2 g, 11 mnl) zn CHCI 3 (20 mL) at -78"C was treated wdh IF (6 42 g, 44
mrrl) and the reaction was monitored by GC (5% SE-30 column) There was obtmned 1 23 g
of 4 (65%), and 10-15% of 2-1odo denvatlve 5
S O M M E L E T Aldehyde synthesis
Aldehyde synthem from primary alkyi halk:les with hexamethylene tetramine.
CH;,Br CHCI H20 HO
CO,Vie , , CO,Me
1 2 (54%)
Me Me
Me" N Me"  ()
I Im, M. C.R. 1 913 157 852
2" let, M. Bull. S Chlm. Ft. 191 3 13 1085(4)
IL . Chlm. Ft. 1 9 70 1445
3 , M.C.
4 , S.J. O.Rea 1954 8 198
2-Carbomethoxy-3-formylluran (2). 3 To a suspension of hexamethylene tetramine
(62.5 g, 0.588 tool) in CHC b (500 mL) was added 2-carbomethoxy-3-bromomethyffuran 1
(120 g, 0.541 tool) After 4 h reflux the complex was filtered and refiuxed for 30 rain in water.
After cooling there was obtained 46 g of 2 (54%), mp 36'C.

354 Name and Unnamed Reacdon Name ad Unnamed Reactions 35 
S 0 M M E L E T - H A U S E R /vnmordum ylid rearrangement
Rearrangement of qualerna/arrrnonium ylids to amines by a Vansfer.
s o N N - M U L L E R Aldehyde synthesis
Ndehyde synthesis from amides or ketoximes, by reduction of imlno chlorides.
C,---C,H, eC'____.L.__ C,---C,H, , ....
NOH N
OPCI C Hs
1 2
1 Sommelet, M. C.R. 1937205 56 1 Sonn, A.,Muller, E Chem. Ber 1919 52 1929
2 Hauser, C.R. J.Am.Chem.Soc. 1951 73 4122 2 Coleman, C.R J Am. Chem Soc 1946 68 2007
3 Huisgen, R. Angew. Chem. 1960 72 315 3 Ferguson, LN ChemRev 1946 38 244
4 Salo, Y. J. Org. Chem. 1967 52 1844 4 Mossetig, E Org. React. 1954 8 240
5 PIne, S.H. Org. React. 1970 18 404
Ethylmethyl-o-xylylamlne (5) and Ethylmethylphenethylamlne (6).4 1 (0.242 g, 2
mmof) and 2 (0.122 g, 1 mmol) in DMSO (1 mL) were heated a1140°C for 3-17 h, poured into
waller, extracted wdh Et20 and the extract evaporated. The reskJue was trealed with Ac20 (to
remove unreacted amine) and after 3 h 10% HCI was added and the mixture extracted with
Et20. Evaporation afforded 3, bp 111-116"C (16 ram). 3 (0 2 g, 1 mmol) and Et-! (0,465 g, 3
retool) In Me2CO were refluxed for 18 h, cooled and dikJted with Et20 to give clals of 4 0.625
g, (94°/.). 4 (0.724 g, 2 mmol) and CsF (1 5 g, 10 mmol) in HMPA were stirred a120 ° for 24 h,
poured into 2% NaHCO3 (200 mL) and extracted wdh Et20 Vacuum distillation gave 0 622 g of
5 and 6 (86=/.) in a ratio of 97.'3, bp 155°C (160 ram).
Benzaldehyde (3). 2 A solution of benzophenone oxlme 1 (91 0 g. 0 41 tool) in Phil (200
mL) was treated wdh PCI 5 (120 g, 0 58 tool) The solvent and the POCI 3 formed were removed
In vacuum and the residue (2) dissolved in CH2CI 2 (125 mL) was treated with SnCI 2 (300 g, t 
tool) in Et20 (900 mL) and saturated with HCI gas The yellow product obasned was hydmlized
by 4N HCI (1250 mL) Steam distillation and E!20 extraction followed by evaporat=on of the
solvent afforded 41 g of 3 (85%), 10p 87-88°C (15 ram).

356 Name and Unnamed Reactions
Name and Unnamed Reactions
Solkl-lkluid phase S O U L A Phase transfercatalyst
transfer catalyst 2 for allphatic and aromatic nudeophc substitution; also
synerglstk: effect with Cu In UIImann synthesis.
ONa   2
5 (92%)
6
8 (75%)
1 Pederson, C.J. J. Am. C. S 1967 89 7017
2 Le, B. Temn Le. 1969 2885
3 Vle, F. A. Chem. InL
1974 3 814
4 , G. Eur. Pa 1 978 5094
5 u, G. F Pamnt 1 979 16673
6 .G. J..Cm. 1985 50 3717,3721
Trls (3,Xl) smlne (TO2) (2).6 Rey Nel (195 g)  1 (1400 g, 10.4
  at  1  a  of N (51 g)   (2 g per u was ps
  185C f 3 h. n on H 2 w lmned f tr 2 h.  tast w
fer a t flrate dl  ge 800 g of 2 (%),  195C/0 5 mm
Phewnltbenne (5). 4 (32 g, 0 2 1), 3 (23
 chmnze (100 mU) were at to 130oC for 9 h. g' 0 2 1)
eh wh water (100 ),
 up a al,tn from EH affom 39 56 g of 5 (90).
SPENGLER - PFANNENSTIEL Oxidation
Oxklatlon of reductive sugars m alkaline solution with molecular 02
OH OH
=.- HO 0
-- o, H
.
I Sler, o, Pfannembel, A. DRPaL 618164
2 Hardegger, E. He/v Chtm.Acta. 1 962 35 618
3-(ў-O-Glucosldo)-O-arabonlc acid (2). 2 A solution of maltose 1 (18 0 g, 53 mmol) in
wer (200 mL) was added dropwse to a ve/well stirred solution of Ba(OH)2 cwst (20 g) in
water (150 mL), under a flow of 02 In 22 h there were absorbed 1250 mL of 02 (calculated
1250 n.). The mixture was saturated with C02 and filtered through Cstite and 120 mL of
Wofalt KS Concentration under vacuum afforded 17 g of crude 2 (100"/,) Separation of 2
was carded out as the brucate, mp ,, 152-154oc, ()0 "50° (c ,, 0 5 water)

358 Name and Unnamed Reaction
Name and Uanamed Reacnon 359
STAA B Reagent
1.1'-Carbonytd'rnldazole 2 an activating reagent for cad:oxylic acids In formation of esters,
amides, peptldes, aldehydes and ketones via imldazolldas 3.
 R,, N/N EtOH RCO2E
O  H
1 sty, H. Ch. B.
1 58 89 1927
2 Sta. H. s n. 1  5 7 609 75, 
3 Staab, H. $ n. 1  6 2 654 119
4 Koes, T.
.P.Plnt. 18 21 251
5 Ley, S.V. Slen
1  90 255
6 Sta, H. A. Ch. In Ed. 1  6 2 7 351
Vitamin A aldehyde (5).3 4 (1 g, 3.3 mmol) and.22 (490 rag, 3 3 retool) in Et20 (50 mL)
was refluxed under N 2 for 30 rain, treated dopwlse a1-20"C with 0.41 N I-INH4 in Et20 (16 4
mL, 1 68 retool) and diluted Wl Et20 (50 mL). After 30 rain me solvent was removed in
vacuum, the residue taken up in MeOH and treated al 0°C with 10% H2504 in MeOH until the
precctate formed redissolved. Addition of 2,4-DNPH (750 rag) in MeOH (10 mL) yielded me
dinltrophenylhydrazone of 5 =n 56% yield, mp 206-207oC.
STAUDINGER Azlde reduction
Conversion of organic azldes with phosphlnes or Phosphites to Irnmophosphoranes
(l:osphazo compounds) and their hydrolysis to amines.
P(OMo) 2
NC-  NC-N.P(OI)
1 3
Ph-N-SdVi + CIC. CH-O  phP,N.H.C)Sde3
Nj. CH2CH  - COOEr Ph3P
4 H), 20" S (S3"/,)
1 Staudlnger, H. He/v. CJn. Acta. 1 919 2 635
2 Marsh, FD. J. Org. Chem. 1972 37 2966
3 r,R.D.G. Pure and AppI. Chem. 1967 59 485
4 Goioicbov, Yu G. Tetrahedron
1981 37 437
5 Carde, R. Bull. Chem Soc. Fr. 1986 615
Trlmethyl N-cyanophosphorolmldate (3).2 Cyanogen aZlde 1 (7 0 g, 0.1 tool) in MeCN
(40 mL) was added slowly to tnmethyl phosphde 2 (12 4 g, 01 tool) in Et20 (200 mL) with
cooling t 15oc. When nitrogen evolution was complete, me volatlies were removed In vacuum
and me residue was washed with Et20 to give 13 1 g of 3 (80%), mp 56.4 - 56 8°C
Ethyl 3-amlnopropsnoate (5).5 To a 1M solution of 4 m THF (from me bromo ester with
NaN 3 In DM$O) was added a molar equNalent of Ph3P, 1 5 equiv of water and a boding chip (N 2
eVolution) After 8 h at 20°C and evaporation, me residue was treated with Et20-hexane and
Ph3PO was filtered This process was repeated and 5 was distilled t 40.45° and 10.5 ton"
(83%).

360 Name and Unnamed Reactions Name and Unnamed Reacnon 361
8TAUDINGER . PFENNINGER Thltranedioxlclesynthesis
dioxide episulfone synthes=s by reaction of dlazomethane with sulfenes or SO 2
2 Cl + SO i  H=C--CH=
12 OSO 3 (70./.)
1 Slauclinger, H, Pfenn=nger, F Chem Ber 191 8 42 1941
2 Hesse, G. Chem Ber lg57 90 1166
30pdz, G ZNatufforschung lg63 hi8 775
40ptlz, G Angew Chem lg61 77 41
5 F'scher, N H Synthess 1 ST0 396
Thllran-l,l-dloxlde (3).5 A cooled solution ol dmzomethane 1 (9 6 g, 0 226 tool) in ether
(500mL) at .15,C was saturatedwdh S02dngas Evaporetlonof the solventleff8 1 gofa
residue whch after ckstlllatlon afforded 7 35 g of 3 (70"/.). bp 64C (0 3 ram), mp 1C
s T E G L I C H - H A S S N E R Direct esteriflcation
Direct room temperature estenfw.atlon of cadooxylic acids with alcohols, including tell. alcohols
with me help of dioydohexyk:ad:irmde (DCC) and 4.<Mkylammopydo'tne catalysts 3.
0 0
-- "R O
3, I Me oў (Cl-ii), (SO%)
O 3
1 $leglldl, W Jngew Chem Int. Ed 1969 9 961
2 Stegllch, W Angew Chem InLEd 1978 17 522
3 Hassner. A. Tetrahedron 19 78 34 2069
4 Hassner, A. Tetrahedron Lett 1 9 78 4475
5 $1eglldl, W Angew Chem Int. Ed 1976 #7 569
General procedure. I A solution of cad:xlxylў acid (10 retool), N,N-dlcyclohewIcarbodllmlde
(11 retool), alcohol (1 | retool) arid 4.pyiTolldlnopyndtne 4 (R,R. (CH2)4) (1 nl'nol), in Et20 (25-30
mL) was allowed to stand at 20°C a few nnutes to a few days until ester/ration was comldete.
N,N<licyclohexylurea was filtered and the hltrate washed with water (3x50 mL), 5% AcEI (3x50
mL) and again water (3x50 mL), dded (MgSO4) and evaporated in vacuum to afford ttle ester in
60-100% y=eid

362 Name wd Unnamed Re:in Name and Unnamed Reactwn 363
S T E P H E N Aldehyde synthesis
Aldehyde synthesis from nitnles and SnCI 2 . HCI
SnC
  [RCH,.2 SnC; 
I HC,0 o 2
seam il
2 +H  RC3
3
1 Stephen, J. J. Chem. Soc. 1925 127 1874
2 Stephen, T.W J. Chem. Soc. 1956 4695
3 Ferguson, L.W. Chem. Flev. 1946 38 243
4 Moseffig, E Org. FleacL 1954 8 246
Aldehydes, general procedure (3).2 A solution of nddle 1 (1 tool) in EIOAc saturated
wth HCI gas al 0°C is added to a solution of SnCI 2 (1.1 mot) in EtOAc previously sabJrated with
HCI al 0°C. After several hours al 0oC the aldirnlne complex [R-CHNH?j2. SNCI6.2 separated as
pale yellow prisms. The complex was filtered, washed with Et20 and dded over KOH under
vacuum to afford a pure samite of 2. Steam distillation of 2 gave aldehyde 3 in the distillate 
me aldehyde was volalile. Alternatively, the aldehyde was extracted from the residue of the
steam distillate
S T E P H E N S - C A S T R O Acetylene cycloptmne synthesis
Polyacetylene cyclophane synthesis from an Iodophenyl copper acetyllde
2
.
1 Stephens, FIO.,Castro, CE. J. OrgChem. 1963 28 3313
2 Campbeil, I.D. Chem Commmun. 1966 87
3 Sab, H.F_ Chem 8er. 1970 103 1157
4 Staab, H.E. Synthes:s 1 974 424
2.2.2.2.2.2-Met acyclophene- 1,8,17,25,33,41-hexayne (3). 4
m-lodophenylacetylene 1 (104 g, 0 456 tool) In EtOH (1000 mL) was added under stimng to
copper (I) chlonde (45 2 g, 0 456 tool) n aqueous ammonia. Fltraton, washing (water, EtOH,
Et20) and drying gave 51 g of 2 (39°/.) N2 was bubbled through boding pyndlne (800 mL). 2
(4.5 g, 0.172 tool) was added and the mixture refluxed 24 h. After distdlatlon of 500 mL of
pyddine, the solution was poured Into water The precipitate was extracted with boding Et20,
Phil arid PhMe From the last solvent one obtaIns 800 mg of 3 (4 6%), mp 350°C

364 Name and Unnamed Reactions Name and Unnamed Reactions 365
S T E T T E R 1,4-Dk:arbonyl Synthesis
Mc.hael addition of aromatic or heterocyc,c aldehydes (via cyanohyddns) to c(,unsaturated
systems. Also addilon of aliphatic aldehydes catalyzed by thlazolium yllds
NaC . HO CN O
1 2 3 (80%)
,...,,,,.N* Ph 0
4 5 7 (75% I
1 Sletter, H. Angew Chem. 1973 85 89
2 Slatter, H Chem. Ber 1974 107 210
3 Sleler, H. Synthesis 1975 379
4 Sletter, H. Angew Chem. Int. Ed 1 976 15 639
5 Sletter, H. Org. Synth. 1 985 65 26
4"Oxo-4-phenylbutanenltrlle (3).(Ar=Ph).4 A solution of benzaldehyde 1 (10.6 g,
0 t mo) in DMF (50 ml.) Is added Over 10 mn to stilted NaCN (2 45 g, 0 05 tool) In OMF (50
mL) at 35°C After 5 ITn aclondnle 2 (4 0 g, 0 075 tool) in DMF (100 mL) is added over 20
 at 35°C After 3 h stimng and work up, one obtains 9 5 g of 3 (80%), bp 114°C (0 3 torr),
mp 70oc
S T I E G L I T Z Rearrangement
Rearrangement or nng enlargement of amines via nitrenes.
(C.H s ) . C_,HS Pb(OAc), (C.H s,C. N- 
NHI 4 Phil, A, lh 5(85%)
t Sheglitz, J. Chem. Ber. 1913 46 2146
2 Stieglitz, J J Org. Chem 19 36 1 31
3 pinck, LA. JAm. Chem Soc 1937 59 8
4 Slat,A.J J. Org. Chem 1974 39 3932
5 Robertson, Chem. Rev 1935 16 417
Phenylphenanthrldlne (3). 3 Amine hydrochiodde 1 (2.72 g, 9 28 mrnol) in EtOH (75 mL)
was treated with 0 926 N cold solution of KOCI. Colorless crystals appear The mixture was
shaken for 30 mm in ice, water was added and the product was filtered and dted (P205) to
afford 2.7 g of 2 (100%), ITў) 102°C (hexane) 2 (2 0 g, 6 8 retool) in anh pyndine (20 mL) was
Veated with an excess of NaOCH3 (exothermlc) After 20 h the solvent was removed in vacuum.
the residue triturated with Et20 and the extract treated with dly HCI to ob(am the hydrochlonde
of 3, mp 107-108°C (from petroleum ether), mp 95-100 ° (Irom water)
Dlphenylmethyleneanlllne (5). 4 To a suspension of lead tetraacetate (4.9 g, 10 mmol) In
Phil (100 mL) under N2 was added a solution of tnphenylmethytamlne 4 (2 6 g, 10 mmol) In Phil
(100 mL) dropwlse under stirring The mixture was refluxed for 1 h, cooled, filtered, washed and
the solvent evaporated The residue was cPstalhzed from EtOH to give 2 2 g of 5 (85%), mp
111-112oc.

366 Name ond Unnamed Reccxion Name wd Unnamed Reacdon, f 367
STILES - SlSTI Formylaflon
Synthesis of aldehydes by formylatton of C.ignard reagents with p-
dlmethylamlnobenzaldehyde and a dtazonium salt.
( NMe=
4 (e/.)
1 Stiles, M., Siati, A. J. Org. Chem. 1 6 6 0 25 1691
2 SistI, A. J. Org. Chem. 1962 27 279
3 $istl, A. J. Chem. Eng. Data 1664 9 108
Cyclohexanecarboxaldehyde (4).2 A solution of sulfandic acid 3 (100 g, 0 31 tool) in
water (200 mL) and Na2CO3 (18 4 g, 0.18 mol) was ўMzottzed with HCI (64 mL) and NaNO2
(24.4 g, 0.35 tool) in water (75 ml.) at 0-5"C NaOAc (70 g) inwater (200 mL) was added to
buffer the solution to pH=6. A solution of P-dlmethylamlnophenylcyciohexyl carbmol 2 (45.8
g, 0.2 mol) In acetone, obtained from cyclohexylmagnes=um bromide 1 and p-
dlmethylammobenzaldehyde, (250 mL) was added. The red solution was stirred for 30 rain at
0-5C and for 3O min wthout coo,ng. The reaction mixture was diluted with water, extracted
with Et20 and the extract distdled to give 15 45 g of 4 (69%), 10p 50-53oc/20 mm
S T I L L E Cross Coupling
Coupling of organotin reagents (and Pd catalyst) wth a or vinyl heMes or triflates, acyl
dondes or a,yt acetates.
1 2
3 (91%)
Pd 1111 
4 6 (7t%)
1 SIIIle, J.K. J. Am. Chem. Soc. 1984 106 4630
2 SIIile, J.K. J. Org. Chem. 1990 55 3019
3 Stille, J.K. Angew. Chem. Int. Ed. 1 9 8 6 25 506
1.Vlnyl-4-tert-butylcyclohexene (3). 1 To t,CI (0 56 g, 13 retool) and tetrak=s
(triphenylphosphine) palladium (0) (0 032 g, 0.028 tool, 1.6 tool%) under Ar was  THF (10
mL) followed by a solution of vinyl tnflate 1 (0.51 g, 1.8 retool) and tnnyltin 2 (0 56 g, 1.8
mmol) in THF (10 mL). The slurp/was heated to reflux for 17 h, cooled to 20°C and diluted 
pentane (60 mL). The rmxture was washed wdll 10% NH4OH solution, dried (MgSO4), liltered
through a short pad of silica gel and the solvent evaporated In vaccum to afford 0.26 g ol 3
(91%)
(2E,6E)-I -(4-Melhyl-2,6-dlmet hoxyphenyl)-3,7,1 l-trlmethyl.2,6,10-dodeca-
trlene (6). 2 From 5 (1.57 g, 5 mmol), Irans, trans-lamesyl acetate 4 (1 32 g, 5 retool), LICI
(0 632 g, 15 mmol) and (ls(de)enz'/lldeneacetone)palladlum (0 144 g, 0 25 tool, 5 moP/.).
Colurnn chromatography (silica gel, 5% EtOAc/hexane) afforded 1 26 g of 6 (71%), Rf - 0 63

368 Name and Unnamed Reacton Name and Unnamed Reactwn 369
S T I L L E Carbonyl Synthesis
Synthesis of awl ketones or aldehydes from apI tnllates or Iodides and organo stannanes in Ihe
presence of CO and a palladium catalyst
(PhP),zPd
p-MeOCs I + CO + BSnH, CO "- pMeO C-.sH4 Clio
1 2 (77%)
O
M=O" " MO- 
3 4 5 (s/.)
1 Stllle, JK J Am Chem Soc 1983 105 7175
2 Stllle. JK J Am Chem Soc 1987 109 5478
3 Stllle, JK J Am Chem Soc 1988 110 1557
p-Methoxybenzaldehyde (2) 1 p Methoxylodobenzene 1 (234 mg 1 retool) in Phil (4 0 mL)
and tetrakzs(tnphenylphosphlne)palladium (0) (35 6 rag) were maintained under 1 atm of CO at
50"C A solution of tnbutyltm hydnde (350 rag, 1 1 mmol) was added wa a synnge pump over 2 5 h
Tnbutyltln halide was removed and punficatlon by chromatography afforded 104 mg of 2 (77%) (CG
yeid 100%)
(E)-l-(p-Methoxyphenyl)-3-phenyl.2.propen.l.one (5) 3 To 4 methoxyphenyl tnllale 3
(390 rag, 1 52 mmol) m DMF (7 mL) were added (E) phenyl tn n-butylstyP/Istannane 4 (645 rng
1 64 mmol) LICI (200 rag, 4 72 mmol) dlchloro 1 1 bls(dsphenylphosphlno) lerocene palladium
(llyPdCI2(dPpf)l(45 rag, 0 06 mmol), a few oystals of 2 6-dz ted butyl 4 methylphenol and 4 A
molecular sieves (100 rag) The n'zxture was heated at 70"C under CO (1 atm) Work up after 23 h
and chromatography (hexane EtOAc 20 1) afforded 246 mg ol 5 (58%) mp 105 106°C
S T O R K Enamlne alkylation
0 A-ylatlon and acylatlon of ketones via enammes or imlnes Also Michael addition via
enamlnes
R N oR 0 o 0
v TEA
1 3  5 0'o%)
 N NH z .
2 6NHCI
1 Stork. G J Am Chem Soc 1954 76 2029
2 Hunlg S Chem Ber 1982 95 2493
3 HIckmoff PW Tetrahedron 1982 38 1975
4 Kneblne M F Synthesis 1970 510
5 Stork G J Am Chem Soc 1971 5939
N-(1.Cyclohexen-l-yl)morphollne (3) Cyclohexanone 1 (19 8 g 0 2 tool) morpholine
2 (19 08 g, 0 22 mol) and TsOH (catalyst) in Phil or PhMe was relluxed with a Dean Stark unit
After water was removed azeotrophlcally distillation afforded 28 g of 3 (85%) 10p 117 118°C
:l.(L10.Undecenoyl)cyclohexanone (5) 2 To 3 (18 4 g. 0 11 moo and TEA (15 3 mL.
0 11 moo In CHCI3 (130 mL) was added 4 (20 2 g 0 1 tool) In CHCI3 (90 mL) at 35°C dunng 2
h After 12 h the red solution was relluxed with 32% HCI (50 mL) for 5 h Separation of water
washing and distillation afforded 18 4 g ol 5 (70%) bp 132 136°C (0 003 ram)

370 Name a Unnamed Reactions
Name and Unnamed Reactions
1 Stork, G.
2 Stork, G
3 HuNg, S.
4 Albdght, J.D.
5 Watt, D S
S T O R K Cyanohyddn akylatfon
Conversion of aldehydes to ketones via cyanohyddn derivatives (ehers) by allo/laflon or
Mk:tlael addition: also used with sdyl ethers, dlalkylannonnles (see also Stetter reaction).
KCN .CN CN
• "OEt O,,, 2. CsH,,,Er O,,, ..--.e,,-
1 2 OEt 3 4 (70"/.)OEt 5 (94./.)
6.,. .,. ,r,A
 (75%)
()'/,)
J. Am. Chem. Soc. 1971 93 5286
J. Am. Cherno Soc. 1974 96 5272
Chem. Ber. 1961 114 959
Tetrahedron 1963 39 3207
Org. React. 1984 31 47
1-Nonen-3-one (5). NitRe (2 g), n-Hexyl bromide (2 8 g) and HMPA (3.9 g), were added
s=multaneously to .an LDA suspension (iPr 2 NH, nBuLI) in 5 rn THF at -78°C After 1.5 h at
-78°C and 1 h at 20°C, the mixture was extracted with ether. DistillatiOn gave 2.12 g of 4 (70%),
bp 100-101oc/0.15 ram.
4 (2.12 g) was hydrolyzed wth 5% sulphudc acid (1 mL) in 5 ml. of MeOH at 20oc for 15 rain to
afford 1.49 g (100%) of a cyanohydnn which was taken up in ether and shaken vigorously vwth
0.5 N NaOH (20 mL) for 5 mm. Ketone 5 (0.167 g, 94%) was isolated
STORK Radў cyclizaK)n
Free radical cyclization wdh preferent;-I formation of cyclopentanes.
B, Sn H ,
h AIBN
1 2 3:1 (87%) 3
Bu Sn H
 AIBN, 80*  SnBu
OH (%) 
2 ,G. J Cm. 19e3 105 6765
3 G. JChem. 1967 109 2829
4 ,G. TetmhmnLe. 19ee 27 4529
Olethyl 3-methyl-4-methylldenecyclopentane.l,l-dlcsrboxylate (2) and dlethyl
ўyclohexane-4,4-dlcarboxylate (3). A solUtK)n of brom,:le 1 (200 rag. 0 7 retool) in Phil
(34 mL), AIBN and 1 1 equivalent of tnbutylstannane protected by a foil of aluminium to prevent
ecattenog of the light was Wmdiated with a GE 275 W sun lamp. After 3-4 h of heating, the
sok, en was evaporated and the residue was stirred wlth 5 mL of EI20 and 5 rr*. of KF saturated
solution. Separation and chromatography (silica gel 5% EtOAc in petroleum ether) gave a
nlXture of 2 and 3 of 3"1 in 67% yteld and 13% recovery of 1 While reflux with 0 02 M Bu3SnH
in Phil gave a 3"1 n'dxture of 2:3, reflux with 1.7 M Bu3SnH in Phil led to a 97.3 mixture of 2:3

372 Hame and Unnamed Reac:ots Name and Uwumed Reacwts 373
S T O R K Reducttve cyclzatton
Cydization of acetylemc ketones to  alcohols by one electron rўtk)n with LI/NH3. also
electrochemically (Shono) or by Sml 2 (Molander)
H
0 (NH.O 4 0
1.)
THF
1 2 (89%)
1 Stork, G J Am Chem Soc. 1965 87 1148
2 Pradhan, SK JOrgChem 1976 41 1943
3 Stork, G JAm Chem Soc 1979 101 7107
4 Shono, T Chem Left. 1976 1233
5 Molander, GA JAm Chem Soc 1989 111 8236
4-Methylenecholestan.5-Ol (2) 2 Naphthalene sodium (from naphthalene (9 6 g, 75
minor) and Na (2 9 g, 130 mmol) m THF (100 mL) 1o give a 0 6 N solution) was added fo a stirred
solution of 1 (198 rag, 0 5 retool) m THF (3 mL) to a faint green end point Approximately 2 mmol
of reagent was consumed per mmol of 1 Work up and chromatograph (alumina Pentane) gave
20mgofl and 160 mg of 2 (89%), ()D=+21O(c0 11)
S T O R Y Macrocy@e synthess
Synthesis of large dng alkanes and lactones from smaller dng ketones via peroxides
( + (C
5 (14%) 6
1 Stow, P R J Am Chem Soc.
1968 90 817
2 Ston/ PR US Patent 1970 3528896
3 Stoly P R J Org Chem 1970 35 3059
4 Stoly P R Synthesis 1970 181
5 Stow PR J Org Chem 1974 29 3463
6 Ston/ P R Synthesis 1975 159
Cyclotetradecane (5) and Pentadecanollde (6) 4 1 (2 94 g 30 mmol) 90% H202 (2
mL 60 retool), MeCN (30 mL) and 7(P/e HCIO4 (6 drops) was stirred at 25°C in an open dish for S
hto give a sold washed with ice water (4O mL) Crystallization (haxane) gave 3 88 g of 2 (95%),
mp 63-84oc A mixture of 2 (75 80 g 268 retool) 3 (140 7 g, 1 67 tool) and anh CuSO4 (95 g)
was stiffed at 25°C lot 13 d Water was added the product filtered and clysialllzed from MeOH
gave 54 78 g of 4 (58%) mp 65 67°C
4 (49 0 g, 149 tool) was thermoiyzod in refluxmg n-decane (720 rnL) for 3 h The solvent was
evaporated In vacuum and the product dlsblied on a splnmng band column to afford 4 4 g ol 5
(14%) 10p 77 78°C (0 3 mm) and 6 62 g ol 8 (18%) bp 110 114°C (0 3 mm)

374 Name and Unnamed Reactions Name and Unnamed R eactwns 375
s T R E C K E R AmlnoacKI synthesis
Synthesis of (z-amino aCKIS from aldehydes or ketones via ўyanohydrlns
• .j "' o.,o
cOOH 4
0, 
1 Strecker, A. LebgsAnn. 1850 75 27
2 Pollard, C 8 J.Am Chem. Soc. 1955 77 40
3 Welnges, K. Chem. Ber. 1971 104 3594
4 Stoul, O J. OrgChem. 1983 48 5369
5 Georgzades, M P Synthess 19 89 616
6 Mow17,0 T. Chem. Rev 1940 42 236
(S)-a-Methyl-3,4-dlmethoxyphenylalanlne (5).3 (4S,5S) 1 (20 7 g, 0.1 mol), ketone
2 (f9.4 g, 0 1 mol) and NaCN (5 4 g, 0 | 1 tool) m MeOH (70 mL) was heated to 60 oc and
HOAc (gmL) was added dm/Ise. The mixture was cooled, filtered, stirred with ware[ (100 mL)
for 1 h and filtered Crystallization from MeOH afforded 33 6 g (82%) of 3, mp 127- | 28 °C, ((z) D
-+85.7 °. 3 (14 9, 40mmol) was added to cooled conc HCl (100 mL). Nterst,mngfor 1 hat-
5°C. 1 h at 20 ° C and 4 h at 50°C, the rraxture was cooled for 2 h, filtered and recstallized from
MeOH to give 11 6 g (63%) of 4. mp 208oc, (ўў)D = -8 4 °
Heating of 4 with Raney-nckel and 2N NaOH at 120oc for 29 h gave 5 as 5.HCl in 98% yield,
mp 174-175oc, (Cў)D =-4 3 °
S T R Y K E R Regloselective reduction
Regloselective conlugate reduction and reductlve s,lylatlon of (z.-unsaturated ketones, esters,
and aldehydes uszng a stable copper (I) hydrK:le cluster [(Ph3P)CuH6
O l( )Curiae M, .... Sd3l =' ......
1 2
 3 (93%)
o '(P'P)CuHe H ('S%)(: o .............. )
1 Stker. JM Tetrahedron Lett 1988 29 3749
2 Stryker. JM J Am Chem Soc 1988 110 291
3 Stryker. JM Tetrahedron Lett 1989 30 5677
4 Stker, JM TetrahedronLett 1990 31 3237
6-Dodecenal (2). 3 Aldehyde 1 (203 rag, 1 12 retool), chlorotnmethyisllane (366 rag. 3 37
retool) and dry Phil (2 mL) were st=rred for 5 rain under N 2 [(Ph3P)CuH]s (804 mg. 0 41 mm )
ll Phil (8 mL) was added and stirred at 20°C for 3 5 h Hexane (30 mL) was added, the
IXeoptate filtered (Celite) and the solvents evaporated The residue 2 (E Z = 1 1) was treate
With THF (10 mL). and 10 drops of 10% aq HCI and stirred for 30 mln. Extraction wh Et20,
washing (water. bnne) and dlT=ng (MgSO4) gave after flash chromatography, 191 mg of 3
(93%)

376 Name and Unnamed Reacton. Name and Unnamed React'ons 377
$ U Z U K I Vinyl coupling
Diene synthesis via Pd catalyzed vthy] coupling of vinyl I:xxates wth vinyl halk:les
OY OY
I
o: voOҐ o: 6Ґ1
bY ч y Pd (P (Ph =-
1 SuzukI, A Teb'ahedronLett 1979 20 3437
2 Suzuld, A. Teb'ahedronLeft 1981 22 127
3 Suzuki, A Teb'ahedron 1983 39 8271
J A/n. Chem Soc
4 Suzuki, A 1985 107 872
5 }Qshi, Y JAm Chem Soc. 1987 109 4758
6 Suzuki, A Put Appl Chem 1 9 91 63 419
Palytoxyne (3). s To a THF solution of 1 (92 5 mg, 0 14 mmol) (y,,SiMe2 t 8u) (5 mL) was
added 10%aq TIOH (0 93 mL) under Ar Themlxturewasstln.edfocSllmnat 20OandaTHF
solution of 2 (55 3 mg, 01 retool) (Y=SIMe2 t Bu) (1 mL) was added followed by Pd(PPh3)4
catalyst (26 8 mg, 0 025 retool, 0 7 mL) Ater 5 mm stirnng the mixture was diluted with Et20
(10 mL), dded (MgSO4) and filtered through Cekte The cnJde 3 was punfied by sdica gel
preparative TLC to gwe 56 6 mg of 3 (92% based on 2) (Y = SiMe2 t Bu)
$ W A R T $ Halogen exchange
Substitution of chlorine atoms wllh fluorine atoms by moans of SbFs
CcC.CCIF-CCI  ч SbF s  CIzFC'CCIF'CCIF 2
1 2 (7O%)
p.CI.CH4.CCI3 ч SbFs --..-----.i,- p-CI.CeH4-CF 3
3 4 (98%)
1 Swarts, F Bull Acad Royal Beige 18 8 2 24 309
2 Swarts, F Rec 'av Clam 1915 35 131
3 Henne, A I J Am Chem Soc 1841 63 3478
4 FInger, GC J Am Chem Soc 1958 78 8034
5 Finger, G C Org React. 18 4 4 2 49
1,1,2,3-Tetrachloro.l,2,3,3-tetrafluoropropane (2). 3 1,1,1,2,3 Pentachloro 2 3,3-
tnfluoro-propane 1 (213 g 1 tool) was heated In a steel vessel wlth SbF s (10 8 g, 0 05 mol)
From the reactor 2 (bp 112°C) was distilled and 1 was refluxed back (bp 152°C) by laming the
temperature slowly and progressrvely from 125°C to 170°C Finally the temperature was raised
to force out the organic matenal vath a small amount of SbF 5 The distillate was steam distilled
from a 10% NaOH solution to give 117 8 g of 2 (70%) and 15% recovery of 1
p-Chloro.c(,(-trlfluorotoluene (4) 4 A mixture of p-chloro-ў(,( tnchlorotoluene 3 (23 0
g, 0 1 tool) and SbF5 (29 58 g 0 11 tool) was heated until the reaction started After completion
of the reaction the mixture was washed w=th 6 N HCI and dnsd on BaO Distillation afforded 17 1
gof 4 (95%), bp 136 138°C mp 36°C, n) 0 = 1 4463 d = 1 353

378 Name and Unned Reac
$ w E R N Oxkatlon
Oxidation of alcohols lo aldehydes or ketones in the presence of other groups.
OMe I, OMe
o
ph. C=C. (H. CH. CH TFAA
 Ph-cmc. c - CH=.CH
 3 "50°, DMSO  4 (g2%)
1 Swem, o. J. Org. Chem. 1978 41 3329
2 Swem, 0. J. Org. Chem. 1978 43 2482
3 Swem, O. Synthesis 1978 297
4 Maycock, C.O. J. Chem. Soc. Perlonl 1987 1221
5 Tidwelt, T.T. Org. Reac 1990 39 297
Methyl 12-Hydroxy-3-0xodeoxycholanate (2).4 To oxalyl chloride (0.24 g,
retool) and DMSO (0.28 mL, 3.94 mmol) in CH2CI 2 at -60oc, was added rapidly 1 (1.07 g, 1.93
retool) In CH2CI 2 arid the temperature was allowed to rise to -40°C during 15 rain and
ma=ntained for 30 rain at -40oC. Ttriethylamthe (0 89 mL, 6.38 mrnol) was added arid after 5
rnm the temperature was allowed to rise to 20=C. The tnmethylsilyl group was removed with
5% HCI In MeOH (TLC). Dilution with water, extraction wth CH2C 2 and chromatography gave
0.58 g of 2 (74%), mp 137-140oC.
Name and Unnamed Reactions 379
$ z A R V A S Y - S C H  P F Cad)omethoxylatlon
Carboxylatlon of activated CH groups wth MMMC (methoxy magnesium methyl carbonate) 1
(Szawasy) and adrift=on of the resulting actvaled ketones to C-N bonds (Sch0pf)
u  (M.O) ..__ M.O-M-O-C-OM. v, ,,NO,
I 44%) 
4 (63%) H
I szalvasy, s. Chem Bet 1697 30 1836
2 Finkbeiner, H L J. Org Chem 1 9 6 3 28 215
3 SchOpf, C LJebgs Annl 1 959 626 123
4 SchOpf, C Angew Chem 1 9 4 9 61 31
5 Gdsar, J M. Synthess 1 9 7 4 284
Methyl 2-Nltrobutanoate (2). 2 A 2N solut=on of MMMC 1 (100 mL) was heated to 60°C
under a flow of CO2,1-ndropropane (9 80 g, 0 2 mol) was added arid CO2 was replaced by N,
Alter 6 h at 60°C, 32% HCI (60 mL) and ice (75 g) were added, the acid was extracted with Et2)
the solvent evaporated arid the residue esterlfled by MeOH-HCI to afford 6.5 g of 2 (44%), bp
77C (2.5 mm), n 0 = 1.4249
4"(2"Phenylethyl)-(e-(2-pyrrolldlnyl)acetophenone (4).5 1 (2M, 0.4 mol) in DMF was
heated under a flow of CO2 to 120°C 3 (22 4 g, 0 1 tool) was added and all was heated for 4 h
under N 2 at 120"C to allow MeOH to escape The mixture was cooled under CO 2 and &l.
PYrmllne (8 3 g,0.12 tool) was added arid stirred under CO 2 for 40 h. The mixture was poured
into conc HCI (200 mL) arid ice (800 g) to gve after recrystallizatn (iPrOH-water) 20.7 g of
4 HCI (63%), mp 200-201oc (dec.)

380 Name and Unnamed Reactions Name and Unnamed Reacnons 381
T E B B E Olefinatlon
Synthesis of terminal olefine from ketones or esters via a n methylene transfer reagent.
1 2 3 4 5 (9e%)
1 Tebbe, F.N.
2 Pine, S K.
3 Grubbs, R.H., Evens, D.A.
4 Tebbe, F.N.
JAmChem. Soc. 1976 100 3611
Synthess 19 91 165
J Am. Chem. Soc. 1960 102 3270
J Chem. Soc, Chem. Commun 1973 227
p.-Chlorobis (qS-2,4-cyclopentadlen-l-yl)(dimethylaluminium)z-methylene-tRanlum (3). t
Into the stirred suspension of CP2CI 2 1 (62 g, 0.25 moo in PriMe (100 mL), AIMe 3 2
(.Dyrol) (48 mL, 0.5 rnol) is washed with PhMe (50 mL) in a dr/box. The mixture is
stirred 48 h et 20"C (CH4 escapes). The product is filtered through Celite0 the volatiles are
evaporated at 20'C under vacuum. The crude solid is washed with hexane, filtered, dissolved
in PhMe (90 mL) and filtered. The filtrate is treated with 2 (10 mL) chilled to -25°C and the
reddish crystals of 3 filleted under At, 38 g (53%)
2-tert-Butylmethylldenacyolohexane (5) 2 To a solutlon of 2 and tett-butyl cyclohexanons 4
(153 mg, 1 mmol) in dry THF (3 mL) at 0°C is added a toluene solution of 3 (2 mL, 0.5 M, 1
retool). After 15 mzn at 20°C, El2 O (15 mL) is added followed by 10 drops of 0 1 M NaOH.
The mixture is dned (Na2SO4), filleted (celde pad) and evsporaled Chromatography (alumina
2% Et20 in pentane) afforded 144 mg of 5 (96%)
T E E R M E E R DInitroali(ane Synthesis
Gem dlnltrodenvatlves from chloronltro compounds.
/NOz 2 NH OH HCI NOz
2 , N*--O"
• 2. HCI
1 2 (47%)
1 teerMeer, E. DebgsAnn. 1876 181 4
2 Hawthome, MF J. Am. Chem. Soc. 1958 78 4980
3 Kapian, R.8 j..am. Chem. Soc. 1 965 83 3535
1,1.Olnltroethane (2) 2 A solution of 1-chloro-l-nltmelhane 1 (0 313 g, 3 mmol) in EtOH
(25 mL) was added to KNO2 (10 0 g, 0.117 rnol) , water (75 mL). After 1 h at 20 ° this mixture
was added to an K:e cooled mLxture of hydroxylalTzne hydrochlonde (15.0 g, 0 216 tool) m conc
HCI (25 mL) and Et20 (75 mL) The solution was saturated wdll NaCI and the Et20 layer
separated and dried (MgSO4). The Et20 solution was treated wdh a saturated solution of NH3 in
Et20 until separation of NH4CI ceased. The NH4CI was removed by f'dtraton, the solvent
evaporated and the concentrate (10 mL) was extracted with NH4OH. Cautious addificatlon with
HCI under cooling, extraclk)n wdh Et20 and solvent evaporation left a residue which was
dissolved ,n EtOH (0 2 mL) and precodated wth saturated NH3 in Et20 (30 mL). The
Wee,pirate furnished 65 rng of 2 (47%), mp 127-128°C

382 Name and Unnamed Reactions
T E U 8 E R Quinone syhesis
Oxidation of phenoLs or anilines to quinones by means of potassium nitrosodlsulfonate
(Fremys .It).
OH 0
1 cH (so).,o 5 o cH
2 N NaCH
2 (%)
OH O
CH  CH 3
C
' K}'IaPO HC
3 C2Hs O C2Hs 4 (5./.) s
1 Teuber, HI. Chem. Ber 1952 85 95
2 Teuber, HI Chem. Ber. 1953 86 1036
3 Teuber, H.I. Chem. Ber. 1955 88 6O2
4 Teuber, H.I Angew. Chem. InL Ed. 1969 8 218
5 Roth, R.A. J. Org. Chem.
1966 31 1014
6 Z]mmer, H Chem Rev 1971 71 229
7 Kosikowski. A. J Org Chem. 1981 46 2426
Thymoqulnone (2).1 Thymof 1 (0 3 g, 2 mmol) in water (2 mL) was treated with 2N NaOH
(2 mL) and potassium ntrosodisulfonate S (0.54 g, 1 equlv) in water (5 mL), followed by 2
more potions of 5. The yellow od was treated wth 2M AcOH and was extracted w EI20.
Washing the extract with NaOH and waler and evaporation gave 0.31 g of 2 (94 5%), mp 43.
4PC (petroleum ether).
2,6"Dlmelhyl-l-elhyl.4,7.1ndoloqulnone (4).5 3 (1.89 g, 10 retool) in Me2CO.(350
mL) ws added to 5 (10.24 g, 40 retool) in 0 055 M KH2PO4 (60 rnL). Nterl h dilution wth
water, extracn wh CH2CI2 (r0 mL) and chromatography on Finds gave 95 rng of orange
4 (5%), n' 115-117oc (hexane)
Name and Unnamed Reactions
T H I L E - W I N T E R QuInone acefoxylatk)n
Synthesis of triaceloxya derivatves from quenones.
0 OAc
BF3.E,O
1 2(81%) OAc
1 Thge, J Chem. Bet. 1 8 98 31 1247
2 Thlle, J, Winter. E. LebsgsAnn 1900311 341
3 Fieser, L.F J. Am. ChemSo 1948 70 3165
4 Blatchly, JM J. Chem Soc. 1963 5311
$ McOmie, JFW Org React 1872 19 200
T I E M A N N Rearrangement
Beckmann rearrangement of amidoximes to urea derivatives in the presence of acKIs (benzene
sulfonyl chloride).
PhS02C 
Ph-C-NH-CeH,I wr. dtoxan:-- Ph-C-NH-CeHI  Ph-NH-C-NH-CeH
1 3 (75%)
t Tiemann, F Chem. Ber 1681 24 4162
2 Plapner, RF J Org. Chem 1858 21 1188
3 Boyer, J H. J Org. Chem 1870 35 2249
4 Smith, PA.S Org. React. 1848 3 366

384 Name and Unnamed Reactions Name and Unnamed Reacnons 385
T I F F E N E A U Am,noalcohol rearrangement
Catlonlc rearrangement (nng enlargement) of 1,2-am=noaioohols by diazotlzatlon
1 Tdfeneau, M. C R 1 9 3 7 205 54
2 Ttffeneau, M CR 1 941 212 195
3 Padlam, W.E. JOrgChem 1972 37 1975
4 Smith, PA.S. Gig React 1980 11 157
Octahydrophenanthrones (2,3,4).3 9-ClS-Amlnomethyl-l,2,3,4,4a,-cis-ga-cls.
hexahydrofluorene-9-trans-ol HCI 1 (331 7 mg. 1 315 retool) n water (8 mL) was treated wth
NaNO 2 (274 3 rag, 3 965 retool) in water (3 mL) and 1 drop of HCI The mixture was stiffed lot 2 h
at 0 o and 15 h at 25 ° Extraction with Et20 and evaporation gave ketones 2:3:4 in a ratio of
55"0.75, total yield 229 mg (81%)
TI$CHENKO . CLAISEN
Converszon of aldehydes lo esters zn the presence of metal alcoholates
2% AI(OPr}3
2 CH-j-CH2-CH2-CHO CCI---------------- CH,j.CI-I.z.CH2.CH 2.0.I.CI.CH2.CH =
1 2 (91%) O
1 Clasen, L. Chem Bet 18 8 7 20 648
2 Tischenko, W J Russ Phys Chem Soc 1906 38 355,542
3 Ln,I J Am Chem Soc 1957 74 5133
4 Stapp, PR J Org Chem 1973 38 1433
TIPSON - COHEN Oteflnatlon
Com/erson of sugar glycols via epoxides into sugar oleflns.
1 T°sO )CH:!
2 (78"/,,I
1 Ttpson, RS,Cohen. A Carbohydr Res 1965 I 338
2 Fraser-Rled, B Can J Chem 19§9 47 393
3 Radatus, B K Synthesis 1980 47
4 Bloch, E. Oig React. 1954 30 500
Methyl 4,§-0-benzylldene-2,3-dldeoxy-c=oO.eryt h ro-hex-2.enopyrenoslde
(2). 3 A m'ture of methyl 4,6-0-benzylidene-2-0 Iosyl-c=-D-glucapyranosde 1 (87 2 g, 0 2
mo 0, zinc-copper couple (65 g, 1 tool), Nal (150 g, t tool), DMF (500 mL) and
dimethoxyethane (100 mL) was heated to reflux (130°C) for 3 h under efflcent stlmng. The
COOled mixture was poured into water (3000 mL) sted with Phil (1000 mL) and filtered. The
olganio phase and the Phil extract was evaporated to d/ness to give 44 1 g of crude 2
Recrystalltzatlon from 85% EtOH afforded 38 5 g of 2 (78%), mp 118-120°C, [ў=]3D0 = +135°C
(c f 0 CHCI3)

386 Name and Unnamed Reactwns Name and Unnamed Reacuons 3 7
T R A H A N O V S K Y Ether oxKJatn
OxKJatlon of aramaic ethers to cad:lonyl compounds with cerium ammonium ntrate
Ph
p CNH, (NO
M.,N 20"C
h
1
 CCCH 3 Ce(NH4) 2
1 Trahanovsky W S J Chem Soc
2 Jac0bs, P J  Chem
3 Lepage, L & Y Can J Chem
4 Lepage L & Y Synthesis
Ph
h
2 (77%)
O
1965 5777
1976 41 3627
1980 58 1161
1983 1018
1,4-Dlphenyl-l,4-dloxo-2 butene (2) 2 A solution of Ce(NH4)2(NO3)6 (1 2 g. 2 2 tool) in
water (4 mL) was added dmpwlse to a stirred solution of 2 5-dlphenylfuran 1 (0 22 g, 1 retool) in
MeCN (10 mL) The mixture was shn'ed at 25=C for30 mn and was extracted with CHCI3 (3x40
mL) The organў extract =s concentrated and a few drops of Et20 are added to induce
cstalllzahon There are obtained 0 1817 g of 2 (77%) mp 134 135°C
T R A U 8 E Punne synthesis
Pynrradine synthesis from guarame and cyanoacetc ester and punne synthesis from
ammopynmldlnes
OH
/NH z EIO=C\ EtONa NL.I 1) HNO2
H. C ч
I 2 3
OH
4 5(65%)
t Traube, W Chem Bet 1900 331371.3035
2 Traube, W Lseblcjs Ann 1904 331 64t
3 Katntzky A Quart Rev (London) 1958 fO 397
Guanine (5)o 1 A suspension o! guanK:hne HCI 1 (40 0 g, 0 4 tool) In EtOH was treated wth
NaOEt (from Na 9 2 g 0 4 at g) To this solution was added ethyl cyanoacetate 2 (48 0 g 0 4
tool) and the m=xture was heated Io reflux for 6 h The salts were removed by filtration and the
rate was concentrated to dryness The 2,4-d=amino 6-oxypynmdlne 3 after nltrosatlon and
reductmn with (NH4)2S gave 2 4 5 Inamlno 6-oxypynmidlne 4 By refluxlng 4 (10 0 g, 74 retool)
With HCOH (190 mL) for 4-5 h there are obtained 7 8 g of 5 (60 67=/,)

388 Name and Unnamed Reactmn Name and Unnamed Reacnon 3 9
T R E I B S Allyllc oxidation
AJlylic oxidation of a(enes using mercunc tnfluoroacetate wdl allylic rearrangement possible
CCO0 CH:COO" v T
OH
1 2
1 Treibs, W Natul1ssenschaften 1 9 4 S 35 125
2 WToerg, KB JOrgChem 1964 29 3353
3 Arzoumenlan, N Synthesss 1 9 71 527
4 Nasslot, G Synthesis 1 9 74 722
17"Oxo-'**4-androaten-3 6dlol-3-acetate (2). 4 A solution of 17-oxo-,5-androsten .
3ol-acatate I (1 039, 31 retool) arid mercury (11) tnfluoroacatate (3 1 g, 72 mmol) in CH2CI 2
(100 mL) was stirred for 24 h at room temperature The solvent was removed .1 vacuum (6O mL)
and the remaining sokJtion was filleted The fdlrate was washed with 5% NaHCO3 solution, then
with water and aga,n filtered After evaporat=on of the solvent, the crude resKJue (720 rag) was
rec.'ystalllzed from MeOH to give 411 mg of 2 (40%), mp 148-150oc, []n) 5 = +25 ° (CHCI3 c -
1 1)
T R O S T Cyciopentanatlon
Methylenecyclopentane Iormatlon from s,loxymethylallylsdane or acetoxymethyla,ylsdane 4 we 
Mchael acceptor olefzns and Pd catalysts (wa trtmethylene methane equivalent)
Ct,,._l CISiH _ _SCI MeMgBr SIMI KOAc -TMS
Cl TEA. CuCl- CI 78" Cl OAc
1 2 (61%) 3 (81%) 4 (90%)
OMOM MOMO
S02Ph 6 (93%)S0=Ph
1 Trost B M J Am Chem Soc 1 979 101 6429
2 Trost BM J Am Chem Soc 1963 105 2315
3 Trost, BM Angew Chem Int Ed 1966 25 1
4 Trost, BM J Org Chem 1968 53 4887
5 Trost BM J Am Chem Soc 1989 III 7487
2-(Acetoxymethyl)-3-(trlmethylsltyl)propene (4) 4 CI3S=H (27 09 g, 0 2 tool) and 1 (20
9, 0 16 tool) =n Et20 (50 mL) was added under stlmng to Cu2CI2 (0 158 g 1 6 retool) and TEA (28
mL) in Et20 (300 mL) over 4 h After 14 h at 20 ° filtration (At) and d=stdlatlon gave 21 83 g of 2
(61%),bl:)50-54°C(2 ram) 2(359 0 156 mol) "1Et20 (700 mL) at 78°was added dropw=se to
3M MeMgBr (183 mL 0 55 tool) After 1 h at 78°C and 10 h at 20°C, wod up and distlllallon
afforded 20 41 g of 3 (81%) bp 158°C (760 ram) 3 (20 4 g 0 125 mol) and KOAc (49 g. 0 5
tool) =n OMF (200 mL) was heated at 55 60°C for 48 h D=luton with water, extraction with Et2 O
and d=stlllat=on gave 20 97 g o14 (90%) bp 95'C (7 ram)
2-Met hylene-4.(m et hoxymet ho xy)-Sa-(phenylsulfo nyl)-3a-decahydroazu len e
(6) 5 To Pd(OAc) 2 (15 rng 0 06 retool) and P(OtPr)3 (101 rag, 0 487 retool) .1 PhMe (2 mL) was
added 5 (1 05 g 3 54 retool) "1 PhMe (2 mL) followed at 60°C by 4 (0 95 g 5 3 retool) After 40 h
at 80°C chromatography (3 1 hexane EtOAc R 1 = 0 33) gave 1 15 g o1 8 (93%)

390 Name and Unnamed Reacnon Name and Unnamed Reaction
TROST . CHEN Decarboxylation
NI complex catalyzed decad:)oxyatlon of dicaltx)xyilc acd anhydndes to fon'n alenes.
1 2
1 Trost, 8 M., then, F. TetrahedmnLeff. 1971 2603
2 Cramer, R. J Org. Chem.
1975 40 2267
3 Jennings, P W. J. Org. Chem. 1 975 40 260
4 Flood, T C. Tetrahedmn Lett. 1977 3861
5 Rose, J D J. Chem. Soc. 19 50 69
6 Grunewald, G L. J. Org. Chem. 1 978 43 3074
1-Methoxycarbonylblcyclo[2,2,1]hept.2.ene (2).6 To freshly distilled diglyme (75
rnL) was added 1-mathoxycarbonylbc.yclo (2,2,1)heptane-endo-,endo-2,3-dicarboxylc
anhydride 1 (9.45 g. 42 mmol) and freshly prepared dicarbonyl bis(tnphenylphosphlne) nickel
(0) s (5.39 g, 8 retool). The stin'ed solution was heated at reflux and the effluent gas was
collected. Nter 6 h, ca 1880 mL of gas (1 equivalent of CO and CO2) had been collected, the
solvent, codistiillng wdh the product (t0 40°C, 2 5 ram) was removed .1 vacuum. To the
residue was added more diglyme (2x25 mL) and the solution was dlstiiled to dryness. The
comb,ned distillates were poured into water (800 mL) and extracted wdh pentane (4x100 mL).
Washing, drying and evaporation of the solvent afforded 5 82 g of 2 (91%)
T $ C H U G A E F Oefln synthesis
Oleflfl formatK)n (preferentially less substituted) from alcohols va xanthate pyrolysis.
._OH I) CS 2 .__ Oc,,SM e
2) NaOH Mel 
1 2
I Tschugaef, J. Bet 1898 31 1775
2 deGroote, A. J Org Chem 1968 33 2214
3 DePuy, CH Chem Rev 1960 60 444
4 Nace, HR Org React. 1962 12 58
3
3-Methyl-l-butene (3). 2 A mzxture of powdered NaOH (40 5 g, 1 mol), CCI4 (50 mL), Et20
(600 mL) and isoamyl alcohol 1 (89 0 g, 1 tool) was treated with CS2 (76 0 g, 1 tool) for 1 h, then
methyl "1tilde (149 0 g, 1.05 mol) was added Distillation afforded isoamyl-S-methylxanthete 2
was 126 g, (71%)be) 100-102°C (10 ram), n) 0 = 1 5234.
Boillr of 2 under partial reflux for 7-8 h was fogowed by distillation and washing with 30"/= NaOH,
then with a saturated solution of HgCI2 RedistdlatK)n of the product afforded 10 5 g of 3 (15%),
bp 19-20oc (760 ram)

392 Name and Unnamed Reacnons Name and Unnamed Reactions 393
TSUJI - TROST AJlylation
Oirecl C-allylation of ketones or of tin enof ethers with Pd(O) catalysts.
1 2 3
4 (74%) (' 
o
Me Pd(Ph=P),= 00 OEt
0 OEt DBLI/PhMeo'c
1 Tsuji, J. Te'ahedmn Left. 1 9 65 4367
2 TsujI, J. J. Org. Chem. 1985 50 1523
3 Tsujt, J. Acc Chem Res 1959 2 144
4 Tmst, B. J. Am. Chem. Soc. 1973 95 292
5 Trost, B. J. Am. Chem Soc 1980 102 5699
6 Trost, B. Acc. Chem. Res. 1980 13 385
7 Uka=, T J. Organomet. Chem 1 9 7 4 65 235
Geranyl acetone (4).2 To Pd2 (dba)3 CHCI3 37 (52 mg, 0 05 retool) and dppe (78 rag, 0 2
retool) in THF (4 mL) was added dropwzse methyl geranyl cad0onete 1 (427 rng, 2 retool) folowed
by methyl acetoacetate 2 (925 rng, 8 retool) in THF (2 mL) After 3 h stlrrfng at 50°C under
the solvent was removed in vacuum, the product was treated wth 10% NaOH (10 mL) and
MeOH (10 mL) and stirred at 20C for 18 h Extraction with 3N HCI and CH2CI2, evaporation,
refluxing the residue for 1 h with Phil (10 mL), evaporation and chromatography
(SiO2Et20"hexane) afforded 288 rng of 4 (74%), 92% E
U G ! Condensation
Pepde synthesis via a three or four component condensation (amino acid, Imine and
isocyanide)
iPr-CH-CO2H ч Ph-C=N-CH2Ph +  N-CHzCOOMe
/
NHCbz Ih 2 3
NHCbz Ph H
4 (63%)
1 Ugi, I. Angew. Chem 1 977 89 267
2 Yamada, T J Chem Soc Chem Commun 1984 1500
3 Yamada, T Chem Lett 1987 723
4 yamada, T J Chem Soc Chem. Commun 1990 1640
Peptlde (4). 4 A mixture of N-carbobenz,/Ioxy-L-valine 1 (1.104 g, 4 4 mmol), Schff base 2
(1.139 g, 4 4 mmol), methyl isocyanidoacetate 3 (0 433 g, 4 4 mmol) in CH2CI2 ( 4 mL) was
compressed for 14 days at 9 kbar Evaporalon of Ihe solvent and chromatography afforded
1.675 g of 4 (63%), mp 126-127°C, o5= -16 0" (c 1.0, CHCI3) The original reaction
employed four components, in place of 2 the reagents were benzylarnlne and benzophenone

394 Name and Unnamed Reactions Name and Unnamed Reactions 395
ULLMANN - FEDVADJAN Acnd'mesynlhesis
Synthesis of polynuclear pyridines from an,lines, phenols and formaldehyde
1 2 3 (46%)
1 Ullmann, F..Fedvadjan, A.Chern. Ber. 1903 36 1027
2 BuuHoi, NP. BullSoc. Chlm. Fr. Mem. 1944 11 406
3 BuuHoi. NP. J. Chem Soc. (C) 1967 213
Benzo-(a)-pyrldo-(4,3,h).acddine (3).3 To • rraxture of 5-an'.noiso 1 (1 5 g, 11
mmol) and 3-naphtol 2 (1 5 g, 10 mmol) hested to 250°C, was added .1 small podons
pamformaldehyde (0.45 g, 150 mmol); when stesm had ceased to evolve, the mixture was
healed for a few more minutes then fmcflonated in vacuum. The thick msn (bp 290°C-11
ram) was collected and recrystelllized from BuOH. A final pudf'kcaflon was effected by
vecuum sublimation to afford 1.3 g of 3 (46%), mp 289°C.
ULLMANN - GOLDBERG Arometicsubsltutlon
Cu ceta}yzed substitution of aromatic hales in the synthess of disryls, daryl ethers, dial
amines, phenols
O O
NH  N
+ Br
1 2 3 (92%)
p - I - Cell4- N(SMe'3)2 Cu >'-- 
HzN NH
(0%)
PhNH 2 Ph - (OH
Ph-I - Ph-O- Ph
Ph-NH-Ph - Cu 210 ° Cu
6 (86%) S 7 (94%)
1 Ullrnann, F
2 Goldberg, I.
3 Renger. B
4 Schulenburg, J W
5 Yemamoto, T
6 Bunnall. J F.
Ber 1903 36 2389
Ber 1906 39 1691
Synthesis 19 6 S 856
Org React 1965 14 19
Can J Chem 19 8 3 61 86
Chem Rev 19 51 49 392
2-Oxo-l-phenyltetrahydropyrrole (3) 3 I (17 00 g, 0 2 mol), KOAc (24.5 g. 0 25 mol) end
copper activated catalyst RCH 60/35 (3 00 g) In 2 (2O0 rn) was reftuxed 4 hr After cooling
and filtration, the fillrele wes washed with 5% NH4OH and weler, evaporated end the residue
(31 g) stirred with hexane to give 29 5 g of 3, (92%). mp 65-67"C.
DIphenylamine (6). 5 Aniline (93 rag, 10 retool), 5 (408 rag, 20 retool) and copper (1 9 g, 30
retool) were healed to 210°C for 12 h Work up afforded 145 rng of 6 (86%), mp 53°C

396 Name and Unnamed Reactions
Name and Unnamed Reactions ,97
V A N B O O M Phosphorylatlng reagent
Phosphorylaton of sugars or nuclaosides by means of sallcylchlorophospite 2.
O
o. r 2 'c'L'
o
1 3
 o.  o-P-o.
R. 404'-Dlmelhoxylntyl
1 Anshutz, R. Liebigs Ann. 1 5 5 7 239 301
2 Young, R.W. J. Am. Chem. Soc. 19 5 2 74 1672
3 Van Boom, J H. Rec. Tray. Chlm. 19 5 6 105 510
4 VanBoom, J.H. Teb'ahedronLett 1956 27 2661,6271
5"Dlmethoxytrltyl-2'-deoxytllylmldlne.3,.phoaphate (3).4 A solution of 1 mmol of
1 (T-thymine, DMT-4,4'-dimethoxytrityl) in dioxane (8 mL), wddine (1 mL) and a slight
excess of 2-chloro-5,6-benzo-l,3-dioxaphosphodn.2.one 2 ( 1 mL of a 1.25 M solution in
dioxane) was stirred at 20oC After 5 mio TLC indicated complete conversion of I into 3 with
zero mobility. Water was added and after wed( up 3 was isolated in 88% yteid.
VAN LEUSEN Reagent
A one-step synthesis of nltnles from caltx)nyls by a reductlve cyanation with tosylmethyl
socyanK:le (TosMIC), also synthesis of 1,3-azole or of ketones
t BuOK H
+ To CHzN===C -
1 2 3 (90/.)
base
T°s'CH2"N === C 
t van Leusen, A M TetrahedronLett 1973 1357
2 vanLeusen, AM. JOrg. Chem. 1977 42 3114
3 vanLeusen, AM Synth Commun 1950 10 399
4 van Leusen, AM Lect. Heteroc Chem 1980 V S-111
5 vanLeusen, AM Org. Synth 1977 57 102
2-Cyanoadamantane (3). 2 To 1 (15 0 g, 0 t reel) and TosMIC 2 (25.0 g, 0 13 reel) |n 1,2-
dmethoxyethane (350 mL) and anh EtOH (10 mL), under cooling was added SOIK:I t-BuOK
(28 0 g, 0 24 moo in portions Slimng was continued for 30 mm at 20°C, then 30 min at 35
40°C Alter filtration and concentration el the filtrate, the product was filtered through a 5 cm
alumina (ca 200 g) layer and eluted with petroleum elher Evaporation afforded 14-15 g of 3
(87-93%), mp 160-180°C (sealed tube)

398 Name and Unnamed Reactions Name and Unnamed Reactions
V E O E J S Hydrox'/latlon
Oxidation of ketones to (z-hydroxyketones by means of a peroxyrnolybdenum reagent.
O O
C ssH Hs MoOPH 1 CsHs s
2 3 (53%)
1 Vedejs, E. J. OrgChem 1978 43 194
2 Krohn, K. ChemBer. 1989 122 2323
Oxodlperoxymolybdenum (pyrldlne) (hexamethylphosphorlc trlamide)
(MOOPH).(1). 1 MoO3 {30 g, 0.2 moP/and 30% H202 (150 mL) was heated until exothermx:,
kept at 35-40oc by cooling and then by heating for 3.5 h at 40"C. Fration, cooling to 10°C,
addition of HMPA (37.3 g), filtration and recn/staliization from MeOH gave MoOs.H20 HMPA 50
g, (67%). The latter was dehydrated at 0 2 mm for 24 h over P205 to give MoO5 HM PA. When
MoO5 HMPA (18 0 g, 51.9 mmol) in THF (40 mL) was stirred, cooled and pyddine (4.11 g, 51.9
mmol) was added dropwise, MoOPH 1 was filtered, washed, dded and stored with Dnente in a
referator.
6"Hydroxy-4,4-dlphenylcyclohex.2.en.l.one (3).1 4,4-Dlphenylcyclohex-2-en-l-one
2 (124 rag, 0.5 mmol) in THF (61 mL) was added to LDA (0.79 mL, 0.7 N, 0 55 mmol) at -23"C.
After 5 rain ali was added to I (282 rag, 0 65 mmol) ,1THF (10 mL) (olive green). After 5 mirt the
mixture was quenched on sat. Na2SO 3 (3 mL) and separated by PLC to give 70 mg of 3 (53%),
and21 mg of 2 (17%).
VILSMEIER . HAACK - VlEHE Reagent
Formylation of aromatics, alkenes, activated H compounds by Me2PP-CHCI CI- (Vimeier-
Haack) or Me2N+=CCI2 CI- (Vehe) reagent.
CH30
0 DMF PCX3 CH=O
H )S° '= CHO
1 Ph
+ Cl" CHCI3 , , (=N*Mel NMeI
3 4 8 8 (Tt'/*) 
1 ViIsmeler, A, Haack, A. Chem Bet 19 2 7 60 119
2 Krishna-Rao, G.S J. Org Chem. 1981 46 5371
3 Konvar, D. Terahedron Left. 1 987 28 955
4 Ferguson, L.N. Chem. Rev. 1946 38 230
5 Grundmann, A Angew Chem. 1 9 6 6 78 747
6 Vjehe, H.G. Angew Chem. lnt. Ed. 1971 10 575
7 Bergmann, J Teb'ahedron Left. 1986 27 1939
1-Benzyl-6-methoxy.3,4-dlhydro.2-naphthaldehyde (2),2 To 1 (1 g, 3 7 retool) in
DMF (4 rnt.) at 0°C was added dropwse PCI3 (0 5 rnt.). After 10 h at 65°C, P(XI 3 (0.5 mr.)
was again added at 25C and heating was continued for 5 h. Quenching with NaOAc (7 g in
18 mL water) extraction with Et20 and preparative TLC (Phil) gave 0,65 g of 2 (81%), mp 116-
117°C (PhH-hexane).
N,N-Dlmethyl-(2-chloro-l.cyclohexenyl) carboxamlde (6). 6 2 (4 9 g, 50 mmol)
and 4 (17.8 g, 110 mmol) in CHCI 3 (60 mL) was relklxed Ior 3 h until 4 had dissolved and HCi
evolution ceased After half of the solvent was removed, Et20 (40 mL) and petroleum ether
(10 mL) were added to g=vel 1.8 g of S (98%), mp 122-125°C. A suspensK)n of 8 (6.7 g, 27
retool) in water (15 mL) and sold NaHCO3were stirred 30 mln and extracted with CHCI3 to give
3 7 g of 6 (71%), bp 99-102°C (0 6 torr ).

400 Name and Unnamed Reaction
Name and Unnamed Reaction
V O I G H T ўў-Amlnoketone synthesis
Synthesis of 0ў-aminoketones from ўў-hydroxyketones.
Ph-C,.O NH 2 Ph-Me, , "N"  N-C-C -Ph
1 Voight, K. J. Prakt. Chem. 1856 34 1(2)
2 Lutz, R.E. J. Am. Chem. Soc 1948 70 2015
3 Kay, J.A. J. Am. Chem. Soc. 1953 75 746
4 Lutz. R.E. J. Org. Chern. 1958 21 49
V O L H A R D T - E R D M A N N Thlophene synthesis
Thiophene synthesis from succink: acids
H.--H-- COONa PS,o H=C--c--c.-CH
1 2 (44%)
1 Vothardt, J. Chero. Ber. 1885 18 454
2 Undstead, R. J. Chem. Soc. 1937 915
3 Wolff, F-W. Org. Reac 1951 6 412
3,4-OIroethylthlophene (2).2 D|sodum salt 1 095 g, I tool) and phosphorus Pentasulfide
-(245 g) was dlslllled dry under a strearo of CO2 to give 83 g of cn.,de 2, which after 15 h
contact with NaOH and 6 h reflux over Na was distilled to afford 50 g of 2 (44.6%), bp 145-
148oc.
v 0 R B R 0 G G E N Nucleoside synthesis
Synthesis of nucleosides by condensation of sugars wdh sllyl heterocycles and kews acids
such as SrlCI 4 or trimethylsilyt tnflate 3.
os% o
o o.  o, jl
4 (89%)
SzO OBz SzO z
1 VorbrOggen, H Anqew Chem Int Ed 1970 9 461
2 Vorblggen, H J Crg Chem 1974 39 3654
3 VorbrOggen, H Chem Ber 1981 114 1234
4 Schrelber, SI. J Am. Chem Soc 1990 112 9657
5"Methoxyurldlne-2,3,S-trI.O.benzoate (4).3 To 5-roethoxy-2,4-
I:,s(tnmethylsliyloxy)uracll I (11 retool, 34 mL of 0 356 N solution In 1,2-dichioroethane) and 1-
O-acetyl-2,3,5-td-O-benzoyl-, D-rCx)furanose 2 (5 04 g, 10 mmol) In dichidroethane (75 roL)
was added trlmethylsilyl Inflate 3 (12 romol, 22 8 roL of 0 522 N solution in dlchioroethane) and
the mixture was stirred for 4 h at 25=C The clear yeliow solution was diluted with CH2CI 2 (50 niL)
extracted with an x:e cooled solution of NaHCO3 (50 mL) and after washing wth water (2x20 mL),
the organic phase was dned (Na2SO4), the solvent evaporated and the residue recrystallized
froro ElOAc-hexane to afford 5 24 g of 4 (89%), mp 205-207oc

2
Name and Unnamed Reactions
Name and Unnamed Reacnons
W A C K E R . T S U J I Olefin oxicaticn
Oxk:laticn of oleflns to ketones by Pd (11) catalyst.
O 2% (Pd (OAc) benzoqumone
0.24 M HCIO 4
1
2 (lOO*/. GC)
o
o, 0MF, o.
1 Ph, Ilps, F.C. Amerchetn. j. 1894 16 255
2 Tsujl, J. Tetrahedron Left. 19 8 2
3 Smidt, j. (Wacker) Angew. Chem. 23 2679
1959 71 176
4 Tsuj, J. Synthesis
1 984 369
5 Wayner, O.DM. J. Org. Chem. 1990 55 2924
CyclOhexanone (2).3 A nlure of F(OAc)2 (44.8 mg, 0 2 retool), benzoquklone (1.06 g, 9
retool) and an inorganic ack:l such as (HCI, HC.IO4. HBF4 ' H2SO 4 or HNO 3 0. ! M) were dissolved
.1 MeCN (43 mL) and water (7 mL). The solution was deoxygenated with AJ" (mtnmlum 30 nn)
and stin'ed until Pd(OAc)2 had dissolved. Cycichexene 1 (0.82 g, t0 retool) was added and the
mixture was stin'ed for tO rain. Extraction of 2 with hexane or Ft20 followed by washing Wdll
30% NaOH and evaporation of the solvan( afforded 0.98 g of 2 (100% by capillary GC).
WAGNER - MEERWEIN . NAMETKIN Rearrangement
Skeletal rearrangement cartt)ns
8', 25 h
1 Wagner, G. J Rus. Phys Chem Soc. 1899 31 680
2 Meerwen, H. Lleblgs Ann. 1914 405 129
3 Nametkln, SS JRussPhys. Chem.Soc. 1925 57 80
4 Coates, R.M J. Org. Chem. 1 9 71 36 3722
5 Zefirov, NS Tetrahedron 1975 31 2948
6 Crlof, SI. J Org. Chem. 1986 51 4326
7 Pliemlngen, H. Angew Chem. Int. Ed. 1 978 15 293
W A L L A C H Azoxybenzene rearrangement
Acid catalyzed rearran+gemenl of azoxybenzenes to P'hydmxyazobenzenes
"  2
1 Wallach, O. Chem. Ber 1880 13 525
2 Hahr, C S J Am. Chem Soc 1 962 84 946
3 Brigalow, HE Chem Rev 1931 9 139

404 Name aad Unnamed Reacrioru Nmne and Ummmed Reactions 405
WASSERMANN - BORMANN Macmcyclactamsynthesis
Ring expansion sequence of lactarns by reaction with cyclic |mlnoethers folk)wed by reductlve
dng opening to a macrocyclic lactam.
O O
1 2 3 HOc 4
0 0
+MeO A, Ph ph, N"N /
oJ'-R oR o
S 6 (67%) 7 (93%)
R: "' Ph
1 Bormann, D. Chem. Ber. 1970 103 1797
2 Wassermann, H.H. J. Am. Chem. Soc. 1981 103 461
3 Wasserrnann, H.H. Tetrahedron Left. 1953 24 3669
Lactam (-/).2 4-Phenyl-2-azetid|none 1 (2.40 rag, 1.6 mmol) was heated with imlnoether 8
(448 mg, 1.56 retool) in chlorobenzene for 21 h. Wo up gave I:,cycllc lactam 6, mp 195-197C
in 6P/. yield. Treatment of 6 with 3 equiv, of NaBH3CN in acatJc acid at 25°C for 3 h, then at 50"
for 2 h and finally at 25'C for 12 h led to the thilleen-membered ring lactam 7' in 93% yield.
w E E R M A N Degradation
Synthesis of lower homoiog aldehydes from o,-unsaturated caltx)xamdes (via Hofmann
degradation)
1 2 (90%)
3 (70%) 4(19%)
1 Weerman. R A Rec Tray Chlm 1 91 8 37 1
2 Masson, CD J Org Chem 1951 16 1869
3 Lane, JF Org React 1946 3 276
2-Thlenylacetaldehyde (4). 2 To a suspension of 1 (44 0 g, 0 28 mot) in CHCL1 (5O mL)
was added SOCI 2 (70 0 g, 0 63 tool) After 24 h at 25 ° the solution was added to cooled NH4OH
(300 mL) and NaOH (35 g) Fzltralon and washing gave 40 g of 2 (90"/.), mp 152-153°C
To a suspension of 2 (12 0 g, 80 retool) in MeOH (100 mL) was added 0 8 N KOH (150 ml_) and
0 8 M KOCI. The temperature rose to 55-60°C and after cooling crude 3 was filtered and
reclystalllzed from EtOH to give 10 g of 3 (70%), mp 115-116°C
3 (22 0 g, 0 12 tool) |n 5O°/° EtOH (200 mL) was treated with oxalic aCK:I dihydrate (20 0 g, 0.4
mol) and heated on a water bath for 15 rain The solvent was evaporated and the residue steam
distilled. Extracbon of the d|stlllate with EI20 and evaporation gave an o11, whP..h after distlflatlon
gave 2.9 g of 4 (19%), bp 69-74°C (8 ram). semlcarbazone mp 131-132°C

406 Name and Unnamed Reactions Name and Unnamed Reactions
W E I D E N H A G E N Im=dazole synthesL
Imidazole synthesis from a-ketols, formaldehyde and ammonia.
H3C,
I.coNH + H2C = CH -  - CH2OH
 H3c,.N - CH= CH=.  - CH2OH
2 10 O
N H=CO
c.(o)'----'-"
(10%) N==PJ
M /CH=CH=OH
HO" Grit CO CH2 CH'2 CH  HN N
PhCHO
1 Weldenhagen, R. Chem Ber 1935 68 1953
2 Weidenhagen, R. Chem. Ber. 1937 70 570
3 Huebner, C.F. J. Am. Chem. Soc. 19 81 73 4667
4 Schobell, E.S. J.pr. Chem. 1982 18 192
4-(2-Dlmethylamlnoethyl)lmldazole (3).3 To a solutzon of 6% hydroxymethyl vinyl
ketone I (100 mL, 6.0 g, 69 retool) was added a 32% solution of dimethylamlne 2 (12 mL, 85
retool). After 15 mln at 20 °, there was added a solution of Cu(OAc)2 (30 g, 150 retool) and
36=/0 formaldehyde solution (15 mL) in 28% NH4OH (225 mL). The n'xture was kept on a
steam bath for 1 h, the copper salt was decomposed by H20 and 3was separated as the
dlplcrate by addition of picdc acid (I0 g) to the hot solution. There was obtained 3.8 g of 3
picrate (10%), mp 230-232,C.
W E I N R E B Ketone synthesis
Synthesis of ketones from acids, acid chiorldes, ўad0onates via N-methoxyamtdes.
_ M. ,._( M,
COCI + IH - O - Me pyr C-I BuLl
1 2 25. "O-Me
3
• 4 (90"/.)
1 Weinreb, SM. Teb'ahedron Left. 1981 22 3815
2 DeBemardis, J.B. Teb'ahedron Lett. 1984 25 5271
3 LlebeskJnd, L.S. Teb'ahedronLett. 1987 28 1857
4 Welnreb, S.M. J Am. Chem. Soc. 1990 112 2g98
5 Weinreb, S.M. J Org. Chem. 1991 58 2911
Cyclohexyl butyl ketone (4). 1 To acid chlodde 1 (146 rag, 1 mmol) and N,O-
dlmethythydroxyl-amine hydrochioride 2 (67 rag, 1 1 mmol) in EIOH (10 mL) at 0°C, was
added pyridine (185 rag, 2.3 retool). After stirring for 1 h, the solvent was evaporated, bdne
was added fogowed by extraction with Et20:CH2CI 2 (1:1) to give 3 purifed by distillation or by
gel chromatograpby To3 (171 rag, 1 mmol) inTHF (10 mL)was added bytylrdhlum (1 mmol)
and the mixture was poured into a 5% HCI in EtOH at 0°C and partitioned between
Et20:CH2CI2 (1:1). Evaporation of the organic layer and prep TLC gave 151 rng of 4 (9(Wo).

408 Name and Unnamed Reacnon
w E I S S Annulation
Synthesis of fused cyclopentanones (bcycio[3 3 0] octadmnes) or of propellanes from
dlcarbonyl compounds va the double aldol condensation with IEketoesters 2
1 Weiss, U Tetrahedron Left 19 6 8 4885
2 Cook, JM CanJChem 1978 56 189
3 Cook. J M Tetrahedron Left 1991 47 3665
Tetramet hyl 1,5"dlmethyl-cla-blcyclo[3.3.0]octane-3,7.dlone.2,4,6,8.
telracalt)oxylate (3a).1 Blacetyl la (17 2 g. 0 20 tool) was added rapidly to slirred dlmethyl
3-oxoglutarate 2 (70 g, 0 40 tool) and aq NaHC03 (5 6 g .1 400 ml. of H20 ) a pH. 8 3 After
24 h, 3a (62 g), mp 155-158oc was filtered The mother llquor with HCI (pH 5) gave adddlonal
3 (total yield 75%), recr/stalllzed from hol MoOH, mp 155-1570C
|n 3 3] Propellanes (e g 5, 56%) were prepared from 2 wdh edher 1,2-cyciohexanedione 4 or
1,2-cyciopentanedlone foflowed by hydrolysls-decad:)oxylaton
Name and Unnamed Reacton 409
w E N C K E R Aztrldlne synthesis
Synthesis of azlndlnes from 1,2 am|noalcohots
H
HSO4 Na(:H N
(/.)
I-Bu-NH-CH2-H CH;C] Pyr, MeSjH
- = t Bu-NH.CHz.,H CH2CI
1 OH MeSO, CI 2 O Ms
3 (55%)
1 Wencker, H J Am Chem Soc 1935 57 2328
2 Leighton, PA J Am Chem Soc 1947 69 1540
3 Gaertner vR J Org Chem 1970 35 3952
4 Nakagawa, Y Bull Chem Soc Jpn 1972 45 1162
1-terl-Butyl-2-chloromethylazlrldlne (3) 3 1 tell Butylan'uno 3-chioro-2-propanol 1
(79 1 g. 0 47 mol) n CHCI.1 (250 ml.) at 0-10°C was treated wth pyndine (71 g. 0 9 mol),
MeSO3H (36 g. 0 37 tool) and then dropwtse wdh MeSO2CI (57 3 g, 0 46 tool) After 24 h
mng, the mixture was poured nto Ice-water and finally treated wdh Na2CO3 a pH.8 The
CHCI3 layer and the extrac was dried (MgSO4) Evaporation of the solvent (below 15"C) gave
2, cold 2 was added to a stirred solution ol Na2CO3 (53 g), dlelhylenelnamlne (10 g)
(scavenger for epoxlde Impurltlas) and water (400 mL) under cooling in an ice bath After 24 rl
of stlmng the mixture was extracted (Et2 O) and the solvent distilled to afford 40 6 g of 3 (55%
bp 47-48°C/10 ram, n 6 . 1 4454

410 Name and Unnamed Reactions Name and Unnamed Reactions 411
WENZEL . IMAMOTO Reduction
Selective reductns of C-C wlth l.aNl alloy
20 °. h
 (95%)
1 WenzeI, H. /nt.Mt.R 1982 27 140
2 Imamoto, T. J Org. Chem. 1987 52 5695
Gneml procedure.2 LaNIs Ingot (3 g) in an autoclave was evacuated at 0.1 mm, heated to
200°C under H 2 at 30 arm for 10 rain. After cooling to 20°C, the operation was repeated five
times. The autoclave was cooled in dry ice-acetone, H 2 was released and N 2 was introduced.
The organic compolJnd (1 retool) in THF.MeOH (2:1) (5 m{.) was added at -78°C with stirring. The
mixture was stirred under N 2 at 0°C and then at 20oc. The catalyst was filtered, the filtrete
concenITated and the residue purified by preparative TLC on silica gel,
W E S S E L Y - M O S E R Rearrangement
Acid catalyzed rearrangement of dlhidroxyxanthone
MeO 175 o. lh o OH
o OH L o CH
1 Wessely, F,Moser, GH Monatsh. 1930 56 97
2 Wheeler, T.S. J Chem Soc. 1956 4455
3 Molho, D. Bull. SocChtm Fr 1963 603
4 Suscltzky, H. J Chem. Soc Chem. Comm. 1984 2275
WESTPHALEN - LETREE Rearrangement
Cadoocatlon rearrangement of steroidal tert alcohols (seeWagner-Mearwein).
M Me CO Me CO
M MeCO eF 2 (10%)
1 WeslphalenTh ChemBer 1915 48 1064
2 Lelree, H. Chem Ber 1932 7O 1947
3 Mihlna, JS J Org Chem, 1962 27 2807
4 Blunlh, JW Tetrahedron 1968 21 1567
5 Szczepen, W J. Acta. Chtm Hung 1986 123 69

413
412 Name and Unnamed Reactions Name and Unnamed Reactona
w H A R T O N Olefln synthesis
Conversion of (z-hafoketones to oleflns using hydrazne (vla enedinKJes C=C-N=NH). Also
reduction of o}-epoxy ketones to allyl alcohols.
1 2 ((2%)
O
o =-
HOAc . OH
1 Wharlon, P.S J. Org. Chem. 1961 26 3615,4781
2 Wharton, PS J. Org. Chem 1964 29 958
3 Stod(, G. J. Am. Chem Soc 1 9 77 99 7067
2-Cholestene (2).2 To hydrazfne hydrate (13 mL, 0 4 mol), KOAc (2.0 g, 20 mmol) and
cyclohexane (10 mL) strred and heated to reflux was added 2o-bromocholestanone 1 (2.005
g, 4 3 mmol) In cyclohexane (30 mL) over 10 rain. Heating was continued for another 30 ITlin.
Nter wash,'ig (H20) and extraction (EI20) the mixture was percolated through alumina (acid
washed). Evaporation afforded 995 mg of 2 (62%), mp 72-74°C, [C]D = +64 °.
W H I T I N G Dlene synthesis
Dlene synthesis from 2-alkyne-1,4-dols wth LAH.
 clc
oH OH OH
1 3 (74%)
4 (35%)
1 Wting, M.C. J. Chem. Soc 1954 4006
2 Isler, O. Heir Chlm Acta. 1966 39 454
2,6.Olmethylocta.l,3,S,7-tetraene (Cosmene) (4). 1 A solution of ethylmagnesium
bromide (trom 2.5 g Mg 0 1 at g) at 0°C was treated with a solution of 3-methynt-l-yne-4-
en-3-of 1 ( 1.4 g, 14 minor) m Et20 ( 10 mL) Stlmng was continued for 3 h at 0"C, a solution of
-methylacr'aldehyde 2 (3 5 g, 50 retool)  Phil (25 mL) was added and s was
continued for another 5 h Saturaled NH4CI solution was added and after usual woll( up,
there was obtained 1.7 g of 3 (74%), bp 78-80°C/10 "3 film, n} ,, 1 4946
A solution of 3 (3 g, 20 mmoi) in EI20 (50 mL) was treated wdh LAH (2 5 g, 65 retool) in Et20
(200 mL). After 4 h reflux, the cooled mixture was poured on ice and tadarlc acid. The Et20
layer was dried (MgSO4), the solvent evaporated under N2 at -4"C and me residue extracted
with petroleum ether and passed through alumina. After evaporation of the solvent at 0C,
there was obtained 0 8-0 9 g of 4 (33-3P/o), bp 50°CJ 0.2 ram, mp -PC, n 8 - 1.5852 (stal0e
for a few months under N 2 at -60°C)

414 Name and Unnamed Reacnon Name and Unnamed R eactmns 415
W I D E O U I S T Cyclopropane synthesis
Tetracyanocyclopropane synthesis from bromomalomtnle and ketones
HzC CN H3C .OH
/c \ .o 8, HC.  -'-"
c \CN C "/" cB,(CN)
2 1
HOB H3C 1
C - C(CN
HC CN
1 Wldequlst S Arklv Keml Mineral Geo/og 1 937 12,4 8 (22)
2 Wldequlst S Arklv Kenv Mineral Geo/og 1 945 20B 12 (4)
3 Scrlbner RM J Org Chem 1960 25 1440
4 Hart H J Org Chem 1963 28 1220
5 Hart H J Aro Chero Soc 1983 85 1161
6 Hart H J Org Chem 1986 31 2784
1,1"Dlmethyl-2,2,3,3-tetracyanocyclopropane (3) 3 A rolxture of bromomalononltnle
1 (1 5 g 10 mrnol) and acetone 2 (1 0 g 17 mmol) |n EtOH (10 mL) was treated wdh a solution
of KI (3 5 g 20 mrnol) in water (10 mL) at 20°C The product was filtered and recJTstalhze d from
aq Me2CO or EtOH to gve 1 19 g of 3 (70%)
W I L K I N S O N Carbonylaton decarbonylaton catalyst
Rh catalyst for carbonylaton, decarbonylatlon, oxygenation, benzyl cleavage
1 Wilkinson, G J Chero Soc 1 9 6 6 1711
2 TSul I J J Am Chero Sec
1968 90 99
3 Trost, BM J Am Chero Sc 1973 95 7863
4 Reuter, JM J Org Chero 1978
5 Gngg, R Synthesis 1 983 1009
6 Llu, HslngJang Synlh Coromun 1990 20 557
Trls(Trlphenylphosphlne)chlorrhodlum (3)  ro freshly recrystalhzed
trlphenylphosphine 1 (12 g, 19 mmol) in hot EtOH (350 mL) was added RhCI 3 3H20 2 (2 g, 7 6
mrool) in EtOH (70 mL) and the solution was refluxed 30 mln Hot filtration of the red crystals
washing with degassed Et20 (50 roL) and vacuuro drying gave 6 25 g of 3 (88%), mp 157
1580C
3-(Trlmethylsllyl)cyclopent-2-en-l.one (6) 4 3 (Tnmethylsllyl)cyclopent 1 ene 4 (500
rag. 3 56 mmol) and 3 (33 rng, 0 035 romol) were healed at 97°C lot 1 5 h under a flow of 02
Removal of the catalyst and distillation gave 455 roq of 5 (83%). bp 90°C. 9 5 mm
1-Methylnaphthalene (7) 6 Ester 6 (143 rog, 0 5 mmol), tnethylsllane (475 mg 4 1 romol)
and 3 (100 mg, 0 1 romol) in Phil (5 mL) was refluxed lot 30 h under Ar Chmroatography on
slhca gel afforded 46 mg of 7 (65%)

416 Name and Unnmnd Reaction Name and Unnmnd Reactions 417
WILLGERODT. KINDLER Rearrangement
Rearrangement of ketones to amides by heating with suffur and ammonia or amines.
160". 4 5 h
Ph-.CO-CH] + S + NHOH  Ph_CH2_CONH z
1 pyr 2 (81%)
130"  
Ph-CO-CH] + HN'/O + Se .... 
Ph-CH=--C -N O
 3h
1 3 4 (94%) 
1 Willgerodt. O. Chent Bet. 1887 20 2467
2 Kindler, K. LiebsAnn 1923 431 193
3 De Tar, D F. J. Am. Chem. Sc. 1946 68 2028
4 Cavaliied, L. J. Am. Chem. Sc 1945 67 1755
5 Brown, E W Synthesis 1975 358
6 Maeyer, R, Weld, J. Angew Chem. 1964 76 861
7 Wofff, E. Ong. React. 1951 6 439
B Hundt, R N. Chem. Rev 1961 61 52
Phenylacetamlde (2).3 Acetophenone 1 (25 0 g, 0 208 rooF), sulfur (37.5 g, 1 17 at g), NH4OH
(50 mL) and pyridine (30 mL) were heated m a sealed tube at 160°C for 4.5 h After
evaporation in vacuum the residue was leached by boiling with water (500 mL) From the
filtrate on cooling 20 g of 2 separated and a second crop for a total of 22 7 g of 2 (81%), mp
156-158°C There is also obtained 1.2 g of phenyiacetlC acid (4 2%).
Thlophenacylmorphollnamlde 4 6 Acetophenone 1 (12 0 g, 0.1 mol), morpholine 3 (18 g, 0 2
mol) TsOH (0 5 g) and sulfur (3.2 g, 0.1 tool) were heated 3 h at 130°C The mixture was
poured into MeOH (50 mL), COOled and filtered to afford 20 7 g of 4 (94%), mp 79-79 5aC.
WILLIAMS - BEN ISHAI Ammoacidsynthasls
Asymmetric synthesis (Williams) of co-amino acids through C-C bond construction on an
elactrophyllc glyclne template
Ph
Ph OH 1) NH2(H HC I /Ph OH
Ph 2) Pd/C- H 2
3) LGlu
Ph
1 H
PhH OH
NH 2 I Bu
H Ph H Ph OSiMe=
Ph ,
Ph ,
 s°""o cc s° ,_ o s
3 (73%) 4 H "8r
H Ph
PhH ? Pd e I'
6 (78%) 7 (8S%) 96% ee
1 Ben-shai, D J Chem Soc Chem Commun. 1975 349,905
2 Wiliams, R.M. J. Am. Chem Soc 1986 108 1103
3 Tlshler, M. J. Am Chem Soc. 1951 73 1216
4 Williams, R M. J. Org Chem. 1 9 8 6 51 5021
5 Wllllams, RM J. Am Chem Soc 1988 flO 1547
6 Wllllams, RM J. Am Chem Soc 1988 110 1553
2) (Boc)zO/Na HCO3
3) pTs OH/Phil &

418 Name and Unnamed Reactns
Name and Unnarned Reactions 419
(SS,6R)'4"(tert Butyloxycarbonyl)-5,6-dlphenyl.2,3,5,6.tet rshydro.4H.1,4-
oxazlne-2-one (3) 6 A suspension o12 (51 g 239 retool) In THF (1200 mL) was freated w=th
ethyl bromoacetate (60 g, 359 retool) and TEA (49 g, 485 minor) Nter 18 h stimng TEA HBr was
filtered and the filtrale evaporated in vacuum The residue was washed wdh water and recryslsllized
from EtOH (250 mL) to yield 60 3 g (84%) of products To 239 g (60 mmol) of this product in 160
mLot CHCI 3 was added a mtxture ct dl tert-butyl dlcarbonate (34 9 g, 160 mmol), NaCI (32 8 g
minor/and saturated solution of NaHCO3 (160 mL) and the mixture was refluxed for 20 h The
aqueous phase was extracted with CHCI3 and the combined organic layers washed (water) dned
(Ns2SO4), the solvent evaporated and the residue distilled to remove the dl tell butyl carbonate
The crude product was used for the next step Recpjstallized (hexane EtOAc 3 1), mp 60 62°C
• - 20 5" (c 5 5 CH2CI 2 ) To the crude product above (32 g) In Phil (750 InL) was added pTsCH
(1 5 g, 8 minor), the mixture was refluxed (Soxhlet extractor filled with CaCI 2 75 g) for 8 h The sorld
after removal of solvent was dissolved In CH2CI 2 washed (water) and evaporated Recrystalllzati0n
from EtOH (750 mL) gave 20 7 g of 3 (73%)
(3S'5$,6R}°3"Bromo'4"(t-but oxyca rbonyl)-5,6.dlphenylo2,3,5,6.tet ra hyd ro.4H.
1,4-oxazlne-2.one (4) To 3 (50 mg, 0 142 mmol) In CCI4 (15 I111.) under reflux, NBS (28 mg,
0 156 mmol) was added, and the mixture was refluxed for 1 h Filtration and concentration gave
crude 4 as a white solid
(3 R'5$'6R)'4"(t'Butoxycarbonyl}oS,6-dlphenyl-3.[(et hoxycarbonyl)met hyl].
2,3,5,6-tetrahydro-4H-oxazln.2.one (6) To a stirred solubon of crude 4 (226 mg 0 48
mmol) m CH2CI2 (11 mL) was added ketene acetal 5 (450 mg, 2 42 mmol) followed by addito
ZnCI2 (575 mL. 0 44 mmol, 0 76M m THF) After 4 min it was quenched wdh water Radial
chromatography (silica gel EtOAc hexane 1 4) afforded 179 mg of 6 (78=/.)
R-Elhyl asparlate (7}o A solution of 6 (86 5 rag, 0 18 mmol) m THF (2 mL) and anh EtOH (2
mL) treated with PdCI 2 (19 mg) was hydrogenated 24 h at 20°C and 20 psi After usual workup
there are obtained 34 2 mg of 7 (85%), 96% ee
W I L L I A M S O N Ether synthesis
Sytlthesls of ethers from akzoholates w=th alkyl helcles
p-OpI  (:X-I + I , KOH =- p OpI.CH-O 
1 2 & 12 h 3 (55%)
OH P'nH VIIIOH MICN OH
4 (aS'/.)
t W'dllamson, A.W J Chem Soc 1 8 5 2 4 229
2 Gumey, 0 J A[n Chem Soc 1 9 2 2 44 1742
3 Dermer, OC Chem Rev 1934 14 409
4 Kalinowskn/,KO Angew Chem Int. Ed 1975 14 763
5 Nakatsugi, T Synthesis 1987 260
p-Nltrophenyl butyl ethel" (3). 2 To p-ndrophenol 1 (139 g, 1 tool) and KOH (56 g, 1 tool)
In 50=/= EtOH (2000 mL) was added butyl Kx:kde 2 (184 g. 1 tool) In BuOH (200 mL) and the
mixturewas refluxed for 12 h After removal of the solvent, the residue was extracted with F.t20
and the unreacted phenol was removed by washing with NaOH The solution was dried over
KOH and the od obtaIned after evaporation was recrystallized from EtOH to afford 108 g of 3
(S5 3%), mp 32C

420 Name and Unnmned Reacno Name and Unnamed Rea, tmns 421
W I S S N E R Hydroxy ketone synthesis
Conversion of acyl chlorides to functlonallzed (OH, OCH3, OPh, SCH3) ketones by means ol
tns(tnmethyls|lyloxy)ethyle ne 4
C OSIM%
OH (Me3Si)21l.. I IMe3 BuLl
LCOzH .--------e,- OS=Me
2 COW,Me3 
OSM%
1 3 4 (80%)
0
o
1 Wissner A Tetrahedron Lett 19 78 2749
2 Wtssner, A J Org Chem 1979 44 4617
Trls(trlmethylsllyloxy)ethylene (4). 2 To glycohc acid 1 (118 g, 1 55 tool) in pyndine was
added disllazan 2 (260 g, 1 6 moP/under N 2 over 30 rain while the temp reached 75=C Me3SICI
(88 0 g, 0 8 mop/was added at 20°C and alter 1 h work up gave 275 g of 3 (80%), bp 78-
8C/12 mm To 2 (245 g, 1 52 tool) in THF (1200 mL) was added 2 4 M nBuLI in hexane (650
mL)at0°C After30mmat45C,3(275g 1 25 mop/ was edded at 78°over30mn After
another 30 mln Me3SICI (205 g 1 9 mol) was added, then petroleum ether Filtration (Cellte)
and vacuum d|stlllatlon gave 366 g of 4 (100°/,) bp 54 56°C (0 1 ram)
1-Hydroxy-2-nonanone (6) 20ctanoyl chlonde 5 (4 0 g, 24 6 mmol) and 4 (15 5 g, 53
mnp/were heated for 3 h at 95-100°C Dtoxane (25 mL) and 0 6N HCI (10 mL) was added
(exothermlc gas evolution) The mixture was heated for 30 mm at 95°C extracted with Et20
and distilled to afford 3 26 g of 6 (84%), bp 83 85"C40 5 mm
W I T T I G Olefm synthess
Otefln synthesis from phosphorane ylldes (e g 3) with aldehydes or ketones cls oleflns
predominate m ahphatlc systems trans m conlugated olefins
 C..eH,-CH2CI Ph3,. P A CH2Ph 3 BuL  C.,H,= CH
O2N Cell, CH .CH C OMe  | I I
E 5 (89%) -CH--P Ph
t W'dtig G Lleblgs Ann 1 949 562 167
2 W'rttJ G Chem Bet 1 9 61 94 1373
3 Ketcham R J Org Chem 1962 27 4666
4 Angelettl E J Chem Soc Perlun Tr I 1 9 8 7 713
5 Doudon A Tetrailedron 1988 44 2021
1966 5 128
8 Emmons, W Angew Chem Int Ed
7 Muq)hy, P B Chem Soc Rev 1 9 8 8 17
8 Maemker A. Org React 1965 14 333
9 Maryanoff, B E Chem Rev 1969 89 863
trans 4-Nltro.4-methoxystllbene (5)3 Trlphenylphosphlne (26 3 g, 0 I tool) and
I>-nltrobenzyl chlonde 1 (17 2 g 0 1 mop/in Phil (50 mL) were refluxed for 2 h After cooling the
solid was collected and washed with Phil to give 25 g of 2 (58°/=), mp 270 276°C Recrystalflzed
from CCI4 petroleum ether mp 278 280°C
To stirred 2 (4 3 g, 10 retool) in Phil (50 mL) under N2was added Ixlb/hthlum (0 85 g, 13 mmop/
to produce 3 Alter 2 h anlsaldehyde 4 (1 63 g, 12 mmol) was added, the mxture was diluted
with petroleum ether and the dark solid collected Recrystaliizatlon afforded 2 23 g of 5 (89%)
mp 131 132 5"C

422 Name and Unnamed Reactzons Name and Unnamed Reactmns 423
W I T T I G Rearrangement
A stereoselectlve base catalyzed [2,3] s|gmatmp|c rearrangement o allyl ethers to homoallyllc
alcohols (steraoselectve)
Lr
0 0
BuLl 140 N
1 Wdtzg, G
2 W'tig, G
3 Uchikawa. M
4 Marshall, J A.
5 SchOllkopf, U
6 Mikaml, K
7 Br0ckner R
Lleblgs Ann 19 4 2 550 260
Chem Bet 1953 86 151
Tetrahedron Lett 1986 27 4577
J On Chem
1988 53 4108
Angew Chem Int Ed 1 9 6 2 I 126
Chem Lett 1 9 8 5 1729
Contalrte (Darmstadt) 1 9 91 3 3
cls-6-1sopropenyl-3-methyl-2-cyclohexenol (2). 4 2,2,6,6-Tetramethytplperldine 3 2
mL and 2 5 M n-BuLl in hexane 7 9 mL was stirred in THF (20 mL) under N 2 at 0°C and for 30
rain at 20°C This lithium tetramethylpipendide (LTMP) reagent was added to a solution of I (1 0
g, 658 mmol) in THF (20 mL) at 0°C After 14 h at 20°C, the mixture was quenched with water,
extracted wzth Et20 and punfied by chromatography (silica gel, 7-10% EtOAc in hexane), to
afford 0 78 g of 2 (78%)
W O H L - A U E Phenazme synthesis
Synthesis of phenazlne N-oxide from anltlnes and nltmbenzene
NO + KOH powder_._
1 3
1 Wohl. A. Aue W Chem Bet 1901 34 2442
2 Maffey, S Gazz Chlm I1al 1946 76 239
3 Patcher. I J J Am Chem Soc 1951 73 4958
W O H L - Z I E G L E R Bromlnaton
Allyhc or benzylic bromlnaUon or chlonnaton with N bromosuccinlmide (NBS) or NCS
CH 3 CH2Br
1 2 19e'/.)
1 Wohl, A. Chem Bet 1919 52 51
2 Zlegler, K Lleblgs Ann 1942 551 80
3 Dauben, H J Am Chem Soc 1959 81 4863
4 Zalusky. M C Bull Soc Chlm Fr 1970 1447
5 Djerassl, C Chem Rev 1948 43 271
6 Homer, L Angew Chem 1959 7I 349
2.Carbomethoxy.3-bromomethylfuran (2) 3 To 1 (96 g. 0 7 mol) in phil (600 mL) under
reflux and stimng, was added a mixture of N brornosucclnmllde (137 g, 0 76 mol) and berlzoyl
peroxide (3 g) After completion the floating succlnlmlde was filtered Work up gave 151 g of 2
(98%), rec13stallized from EEt20 hexane or sublimation at 60°C (0 1 mm), mp 54"C

424 Name and Unnamed Reactions Name and Unnamed Reactions 425
W O H L - W E Y G A N D Aldose degradation
Degradation of sugar oxzmes via cyanohyclrins by means of an acid chlonde/pyridine (Wohl) or ot
fluorodlnitrobenzene (Weygand).
CH - NOH CN
HO Ph .._._._... BzO MeO(-I O
HO Pyr BzO-- M. "- = NHCOPh
OH Oz HO.-=.- "OFFNHCOPh
"- OH OCOPh
1 2 (65%) 3 (37%)
CH. NOH CN
NO NO= HO
OH ч ,=.c j_oH HO
(H NO= ,_oH
4 5 6 ((;1%)
1 Wohl, A. Chem. Bet. 18 9 3 26 730
2 WohI, A. Chem. Ber. 1899 32 3666
30eferrari, J.O. J. Org. Chem. 1966 31 905
4 Weygand, F. Chem. Ber. 1950 83 559
5 Weygand, F. Chem. Ber. 1952 85 256
1,1-BIs(benzamldo)-l-deoxy.I)-galactltol (3).3 1 (3.92 g, 17 retool) was added to 1:1
pyddlfle: PhCOCI (48 mL) and kept at 100=C by cooling. After 24 h at 20=C, al was poured into
water (400 mL) and 2 was recrystalllzed Irom Me2Co:F.tOH (1:3), 9.45 g (65.6%), mp 190-
191C, ((X)o-+lg-5°(c0.TCHCA3). 2 (4g,4.Smmol)wasstlrredwllhNH31nMeOH(100mL)
for 60 rain. After 24 h evaporatk)n afforded 770 mg of 3, mp 194C; from EtOH 700 mg (37%),
mp 203.204C, (ўz) o . .5.8o (c 0.65 p/r).
Amblno (6),4 CO 2 was bubbled through NaHCO3 (1.5 g, 17 retool) in water (70 mL) and
glucose oxlme 4 (1 g, 4.5 mmo0. At 55-60=C 5 (1.8 g, 10 retool) in IPIOH (30 rnL) was added.
After 1.5-2 h, 420 mgof6 (61%), mp 162 was Isolated.
W O L F F Rearrangement
Rearrangement (nng contraction) of (=-dzazoketones to cartx)xyfK:: adds or thezr derivatives
(esterS, amides) via ketenes (see also Arndt-Estert).
S H
-- 1 2 3 (48%)
O O
RI' R2 2h I:%  Rt N."
! Wolft, / I.lebgs,4nn. 1912394 25
2 Borch, R.F. J. Org. Chem. 1969 34 1481
1961 73 261
3 Cohen, L.A. Angew. Chem.
4 Wynberg, H. J. Org Chem. 1968 33 4025
5 CIssy, J. Synthess 1 9 88 720
6 Meier, H. Angew. Chem /nt. Ed. 1975 I4 32
7 Bachmann Org. React. 1 942 I 39
4.Carboxy.3,3,5,S-tetramethyl-l-thlacyclohexane (3) .4 4-Hydrazo 3,3,6,6-
tetrall-ttdacydohepta-5-one I (4.3 g, 20 mmol) in PI1H (50 mL) was added to active
MnO2 (6 g) and MgSO4 (10 g) in Phil (50 mL) over a pedod of 30 mln. The solution becante
yellow and gas e)lution started. After 24 h at 200C, the mixture was filtered and the fir=rate
concentrated. 500 mg of the residue after reflux with 03 HCI gave 195 mg of 2 (48%), mp
149-152oc. The rest of the residue was dvornetographed (silica gel, PhMe) to give 0.55 g
(16.5%) Of unreacted ketene 2, bp 103-104°CJ12 ram.

426 Name and Unnamed Reactior Name and Unnamed Reactmr 427
WOLFF . KISHNER . HUANG MINLON Reduction
Reduction of ketones to hydrocarbons by heating with NH2NH 2 and aqueous KOH (Wofff-KlShne
or KOH in ethylene glycol (Huang-Mlnlon)
O
PhO HO OH A PhO
1 2 (95%)
O
(H2C)1 (CH2)0 ='- (HzC) (CH2)0
(8%) s
1 Kishner, J J Russ. Phys. Chem. Soc. 1 911 43 582
2 Wofff, C. Llebgs Ann. 1 91 2 394 86
3 Huang Minion J. Am. Chem. Soc. 1 946 68 2487
J Huang Minion J. Am Chem. Soc. 1 9 4 9 71 3301
5 Nickon, A. J Org chem. 1 9 81 46 4692
6 Todd, D. Org React. 1 9 4 8 4 378
Y'(P-Phenoxyphenyl)-butyrlc acid (2). 3 A mixture of Y'(p-phenoxybenzoylproplonic acid 1
(500 g. 1 85 mol), KOH (350 g, 6 25 tool), 85% hydraZlne hydrate (250 mL) and di (or td) ethylene
glycol (2500 mL) was refluxed for 2 h. The condensor was removed and heahng continued until the
temperature reached 195"C. Refluxing was continued for 4 h, the cooled mixture was diluted with
water (2500 mL) and slowly poured into 6N HCI (1500 mL). Flitretion and drying gave 451 g of 2
(95%), mp 64-66C.
WOLFRAM - SCHRNIG - HANSDORF Carboxymethylation
CarboxymethylatK)n of aromatics in the presence of oxidants or photochemcally
ч Cў:H= oCOOH -
1 2 3 (70%)
1 4 3
1 Wolfram, A., Schmlg, L Germ Pat 562 391
Hansdorf, E. U S Pat 1 951 686
20gata, Y J Am Chem Soc 1 9SO 72 4302
30gata, Y J. Org Chem 1951 t6 239
4 Southwlcko P L. Synthesis 1 97O 628
Naphthylacetic acid (3). 4 a) Naphthalene I (56 8 g, 0 44 mol) monochloroacetK: ac=d 2 (14 1
g, 0,149 tool), Fe304 (87 6 rag) and KBr (420 mg) were heated gently for 20 h so that 200"C
was attained after 10 h and 218"C after 20 h. Unreacted 1 was distilled (43 g) and the residue
extracted with hot NaOH solution, rCtered and acidified with HCI to give 19 4 g of 3 (70%), mp
108-113"C. Recrystalllzed from water, mp 124-126=C.
b) To a boding mixture of 1 (25.0 g, 0.2 tool) in Ac20 (150 mL) was added KMnO4 (3 0 g, 0.02
tool) and the mixlure was boiled and stirred for 20 mm Unreacted 1 and Ac20 were removed
by distillation and the residue was steam distilled. The hot solution was filtered and acidified
with H2SO 4 to give 3 (66%) (based upon recovered naphthalene).

428 Name and Unnamed Reacnons
Name and Unnamed Reacnons 429
W O O O W A R D Peptlde symhess
Pept,:le synthess mediated by N-ethyl 5-phenyllsoxazollum-3'-sulfonate 3
H .... CHi-CH-COOH + H.I-CH=-COE, 
EI3N 2O"
1 NH - CO= - CH3 - Ph 2
SO=
NHo CO 2 - CH= - Ph O'Nч_Et
4
Woodward, R B Tetrahedron, Suppl 7 19 66 21
Woodward, R B J Am Chem Soc.
1961 83 1007
Woodward, RB Tetrahedron, Suppl 8 1968 22 321
Carbobenzyloxy-L.asparaglnylglyclne ethyl ester (4). 3 Carbobenzyloxy-L-
asparegtne I (798 rag, 3 retool), oxazolium sail 3 (760 rag, 3 retool) and Et3N (304 rag, 3 mmol)
was stirred for 7 mm in MaNe 2 at 20oC Glycine ethyl ester hydrochrlde 2 (419 rag, 3 retool)
and B3N (304 mg, 3 mmol) were added and the mixture was stm.ed for 24 h at 200C The
solvent was evaporated and the residue was triturated wsth 0 5% NaHCO3 solubon (40 mL)
under heating Cooling and filtration gave 846 mg of 4 (80%), mp 185 5-187°C, recwstallized
from Me2CO-water 4 had mp 186-187°C
W U R T Z Coupling
Coupling of alkyl haides with Na, supplanted by the coupling ol alkyl halldes or sultonates wth
Gngnard reagents or RLI in the presence o! Cu(I) salts
1 CH n H3C CH3 2 (11%)
L,CuCI,
n CH,7-OTs + t Bu MgBr  n Cell,7 C Me3
3 4 (75%)
1 W0.1z.A LleblgsAnn 1855 96 364
2 Badey. WJ J Org Chem 1962 27 3O88
3 Homer. L Angew Chem 1962 74 586
4 Buntrock, RE ChemRev 1968 68 209
5 Kosolapoff, G M Org React 1 9 51 6 326
6 Whitasldes. GM J Am Chem Soc 1969 91 4871
7 Erdlle, E Tefrahedron 1984 40 641
8 Schlosser. M Angew Chem Int Ed 1974 13 82
3,4.Dlmethylhexane (2). 2 To sac butyl bromide 1 (300 g. 218 mol) in Et20 (700 rnL) was
added sodium (50 g, 218 at) and the mixture was refluxed for 56 h Distillation afforded 16 5 g
of 2 (11%), bp 117"C, n = 1 4040
2,2-Olmethyldecana (4) 8 To octyl tosylate 3 (40 mmol) in 50 mL of THF at -78"C was
added tBuMgBr (56 mmol in 32 mL of Et20) and I-P2 CuCI4 (0 2 mmol m 2 mL of THF) The
mixture was warmed to 25"C dunng 2 h and stirred for 12 h Aclddcatlon with 2N H2SO4,
washing (2x50 mL water), drying and distillation gave 5 1 g (85%) of pure 4

430 Name and Unnamed Reacnons Name and Unnamed Reactions 431
Y A M A O A Coupling reagent
Dlethylphosphoryl cyanide 3 as a reagent for amlde bond formation and application to peptide
synthesis free of racemzaton.
O
+ NC-P (OEI)2 / NHCOPh
, v "CO2H H2N''CO=Et -- 3 0 °' INHtcO2Et
O
1 2 4 (86%)
1 Yamada, S Tetrahedron Lett. 1 9 71 3595
2 Yamada, S. J. Am. Chem. Soc. 1972 94 6203
3 Yamada. S. TetrahedronLett. 1973 1595
4 Takar'zawa, A. YakugakuZasshl 1965 851 298
N-BenzoyI-L-leucylglyclne ethyl eter (3). 3 N-BenzoyoL-leucine 1 (0.235 g, 1 mmol)
and glycine ethyl ester hydrochioride 2 (0 1534 g, t.1 mmol) in DMF (10 mL) under stirdng was
treated wdh diathylphosphoryl cyanide 3 (0.179 g, 1.1 mmol) in DMF at O°C, followed by the
addlbon of tdethytamlne (0.212 g, 2 1 mnloq. The mixture was stirred for 30 rain at 0°C and 4 h at
20*C The reaction mixture was diluted with PhH-EtOAc, washed with 5% HCI, water, 5%
NaHCO3 solution and bnne. Evaporation of the solvent gave crude 4 which after silica gel
chromatography afforded 0.271 g of 4 (66%) (pure L), mp 158-160"C.
Reagent 3, bp 93-96"C (14 ram), was prepared by condensation of triethyl phosphite and
cyanogen bromide.
Y A M A G U C H I Lactonlzation reagent
2,4,6-Tdchlorobenzoyl chiodde reagent for estenfication of acids via a mixed anhydride, also
used for large ring iactonlzation with DMAP (see also Steglich-Hassner).
O O
1 3 (46%1
t Yamaguchi, M. BullChem. Soc. Jpn. 1979 52 1969
2 Yonemitsu, O. J. Org Chem. 1 9 9 0 55 7
2,4,6.Tddemethyl.3-deoxymethynollde (3}. 1 A mixture of seco acid 1 (272 rag, I
mmol) and tnathylamme (0 153 mL, 1.1 mmol) inTHF (10 mL) was stln'ed for 10 rain at 20°C,
and then 2,4,6-tdchlorobenzoyl chloride 2 (160 mL, 1 mmol) was added. Nter stirring for 2 h
at 200C, the resultir precipitate was filtered and washed with THF The filtrate was dikJted
with Phil (100 mL) and slowly added to a refluxing solution of 4-dimathylaminopyrldine
(DMAP) (732 mg, 6 retool) in Phil (100 mL). After 40 h the reaction mixture was washed with
citric acid solution, water and dned (Na2SO4). Evaporation of the solvent afforded the cnx:k)
product (247 mg). Separation by preparative TLC (silica gel Merck), Et20 Phil (2:1), gave 116
mg of 3 (4b'%), 85 mg of a dimer (26°/.) and 21 mg of polymer. Re<:ryatalzation of 3 (CH2CI2
/diisopropyl ether) afforded coiodess needles, mp 123"C.

432 Name and Unnamed Reactioas Name and Unnamed Reacno 433
Y A M A Z A K I Cyanoaniline synthesls
Synthesis of o-aminoaryinitnles (useful in pynrnldlne synthesis) from ndroqulnolines, nitro
naphthalenes, and m-substituted (CF3, COCH 3 and COC6H5) ndrobenzenes
1 YamazakJ, M. ChentPharm. Bu# 1981 29 1286
2 YamazakJ, M. Chem. Pharm. Bu# 1982 30 851
3 YamazakJ,M. CherPharmBull 1985 33 1360
2-Amlno-l-naphthlllenecarbonltrlle (3).3 2-Nitronaphthalene 1 (5 19 g, 30 retool)
was added to stirred elhyl cyanoacetate 2 (9 99 g, 90 retool) and KOH (5 04 g, 90 retool) in
DMF (90 mL) and the mixture was sttn'ed for 24 h. After solvent evaporation, the residue was
hydmlyzed with 5% NaOH (60 ml.) for 1 h at reflux. The mixture was extracted with CHCI3.
The CHCI 3 extract was dried over Na2SO4, and concenlrated. The residue was pudfled by
column chromatography on alumina with CHCI 3 as solvent fo afford 3 80 g of 3 (54%), mp
131.5"C. If the reaction was carded out in the presence of KCN the yield rose to 75%.
Z E I S E L - P R E Y Ether cleavage
Acid catalyzed cleavage of aromat=c methyl or ethyl ethers Qusntdatlve methoxy group
determination Also ether cleavage with tnmethylsliyl iodide 6
Ph-OCP a + Ht z Ph-OH + CI AgNO3
pyr HCI 2
Ph- OMe  Ph- OH
1 HOAc 190" 3 (100%)
O
PhO 
17h. 100":
4 5 (99"/-)
1 Zelselo S. Monatsh 1885 6 406
2 Belcher, A. J. Chem Soc. 1957 4480
3 Prey, V. Chem Bet. 1941 74 350
4 Burwel, R.L. Chem Rev. 1954 54 635
5 Ganem, B. J. Org. Chem. 1974 39 3728
6 Jung, M.E. J Am Chem. Soc. 1977 99 968
Aromatic methoxy group determination 1 Arusole 1 is heated in HI (10 mL) and the methyl
iodide which distills ls trapped In AgNO3. The Agl is deterrnlned gravlmetncally.
Phenol (3). 2 Anisole 1 (107 g, 1 mol) and pyndine HCI 2 (130 g, 1.3 moo were heated with
AcOH (5-10 mL) for 5 h at 190"C The mlxtura was poured Into water (500 mL) and extracted
with EI20. From the Et20 soluhons 3 was extracted with NaOH and the alkaline solution was
saturated with CO2. Extraction with ether and distllation of the extract afforded 94 g of 3
(100%), mr) 35-40=C

434 Name and Unnamed Reacnons Name and Unnamed Reacnons 435
Z I E G L E R Macrocyclc synthess
Synthesis of macrocycllc ketones from dtndnles ustng hgh ddutlon
,soprene  O O,INH2
O O 2 I 6NHCL
oOo
3 (85%) 
1
1 Zlegler K Chem Bet 1934 67 139
2 Zingier K Lleblgs Ann 1 937 528 143
3 Newman MS J Org Chem 1975 40 2867
2-Cyano-7,13,16,19-pentaoxacyclotetracosanone (3)3 A suspension of sodium
sand (34 5 g 1 5 at g) in Et20 was Ireated dmpwse with a solution of tsoprene (102 g 1 5 tool)
and N methylanlhne (209 g 1 95 tool) in Et20 (300 mL) A solution o! 7 10 13 16 19
pentaoxapentacosanedlnltrde 1 (56 7 g 0 15 tool) in Et20 (400 mL) was added dunng 24 h
Afler addition heating was continued for another 2 h To the cooled mixture was added water
the product was dlStdled to remove N methylandlne and to leave a resclue (50 g) of a mixture of
2 and 3 From a small amount of this mixture by distillation one obtains 2 bp 235 240°C (0 5
mm) The remalntng crude mixture was shaken with 6N HCI (2000 mL) for 30 mtn Separation in
the usual way gave 49 3 g of 3 (85%) 10p 210 213°C (0 5 ram)
Z I N C K E - S U H L Cyclohexadtenone synthesis
Synthesis of cyclohexadtenones from phenols by Fnedel Crafts alkylaton
OH O
CH
1 2 (72%)
1 Zlncke, Th, Suhl, R Chem. Bet 1906 39 4148
2 Newman M S J Org Chem 1958 23 1236
3 Newman M S J Am Chem Soc 1959 81 6454
3,4.Olmethyl-4-trichloromethyl-2,5-cyclohexadlenone (2) 3 A solution of 3,4-dlmethylphenol
1 (61 0 g 0 5 mol) in CCI4 (300 rnL) was added dropwlse dunng 30 mtn to a slurry of AICI3 (133
g, 1 mol) in CCI4 (300 mL) keep=ng the mixture at 5 20°C, while a stream of N 2 swept the HCI
Iormed into a trap containing a measured amount of NaOH After 2 h, 0 4 mol of HCI had been
evolved and the reaction nxture was poured onto 1500 g of ce containing 32"/. HCI (100 mL)
After usual work up the crude 2, recwstallized from Phil afforded 96 5 g o! 2 (72 5"/.,), mp 60
61°C. ONPH mp 166-167 50C

436 Name and Unnamed Reacnons Name and Unnamed Reactions 437
z I N K E - Z I E G L E R Synthesis of Callxarenes
Synthesis of callxarenes (a basket-like macrocycltc compound)
1 lo*
1 2 3 (S0%)
1 Zinke, A., Ziegler, E. Chem Ber. 19 41 74 1729
2 Comforth, J.W. Br J. Phemlacol. 1955 10 73
3 Gutsche, C D. J. Org. Chem. 1 986 51 742
4 Gutsche, CD J. Org. Chem. 1990 55 4487
5 Gutsche, C.D. AccChem Res. 1983 16 161
6 Gutsche, C.D. Top. Cuff Chem. 1984 123 1
6 Gutsche, C.D. PureAppl Chem. 1988 60 1607
p-tert-Butylўlllx(4)arlne$ (3).3 A mixture of p-tert-btltylphenol 1 (100 g, 0.665 mol),
37% formalin 2 (62.3 mL, 0.83 mol) and NaOH (1.2 g, 0.03 tool) in minimum quantities of water
was heated for 2 h at 110-120"C. The product was dissolved in CHCI3, the solution was
neutralized with HCI, the organic layer was evaporated and the residue was heated in crq::4enyl
ether (800 mL) under a flow of N2 to remove the water. The mixture was heated to reflux tot 2
h and after cooling to 20"C, EtOAc (1000 mL) was added under stin. Filtration and washing
with EtOAc (100 mL) and AcOH (200 mL) gave 66.5 g of 3 (62%). Recyatalllzation from
PhMe gave pure 3, 61 6 g (50%), mp 342-344"C
Z I N I N Benzidlne (semldlne) Rearrangement
Acid catalyzed rearrangement of hydrazobenzenes to benzJdlnes and senlldlnes
Br 1 Br Br Br 2 (75%)
R
H2N
ч
1 Zinin, N. J Prakt Chem 1845 36 93
2 Jakob$on, P. Chem. Ber. 1893 26 688
3 Hammond, G.S. J Am Chem Soc; 1 9 5 0 72 220
4 Ingold, C.K. J. Chem. Soc. 1957 1906
3,3.Olbromobenzldlne (2). 3 A solution of 3,3'.dlbromohydrasobenzene 1 (4.0 g, 11
retoOl) in Et20 (50 mL) was added dropwlse under StilTing to ice cooled conc. HCI The while
precipitate of 2 hydrochioride was liilered. Reaction with 10% NaOH, extraction with Et2 O
and evaporation afforded 3 g of 2 (75%), mp 127-129C.

NAMES INDEX
Acylom 
Akerrnann 117
ALDER (Ene) reaction 1
Alder [;5
AIl=n 321
ALPER Carbonyiaton 2
AMADORI Glucosanne rearrangement 3
ANGELI - RIMINI Hydrox=mў acid synthesis 4
ARBUZOV - MICHAEUS Phosphonate
synthesis 5
ARENS - VAN DORP Cmnamaldehyde
synthems 6
ARNDT- EISTERT Homologatlon 7
ATHERTON - TODD Phosphoramldate
synthess 8
Aue 423
AUWERS Fiavone synlhesm 9
B=chmann 149
Bacldund 309
BAERo FISCHER Amno sugar synlhesm 10
BAEYER Oxndole synlhesm 11
BAEYER Dlaryimeth=ne synlhesis 11
BAEYER Pyr|dme synthesm 12
BAEYER- DREWSON Indoxd synthesm 12
BAEYER o VILLIGER Ketone oxidation 13
BAEYER - VILLIG ER Tntylatlon 13
BAKER- VENKATARAMAN Flavone
synthess 14
BALLY- SCHOLL Benz=nthrene synthesm 15
BALSON AIk3,1atlon 15
BAMBERGER lndazolecleav=ge 16
BAMBERGER Phenylhydroxylamlne
rearrangernenl 17
BAMBERGER Benzotnazlne synthesm 17
BAMFORD - STEVENS- CAGLIOTI - SHAPIRO
Reactmn 18
BARBIER React=on 19
BARBIER- WlELAND Degradation 20
BART - SCHELLER Amonldatlon 21
BARTON Nltnte phololysts 22
BARTON Dearnln=tlon 23
BARTON Decarboxyiaton 24
BARTON- KELLOGG Olefmatlon 25
BARTON- McCOMBIE Deox3/qen=ton 26
BAUDISCH Nltrosophenol synlhesB 27
B=uer 156
BAYLIS - HILLMAN Vinyl alk'yteton 28
Beak 161
BECHAMP Arsonyl=11on 29
Becker 261
BECKMANN Rearrangement or tragment=tlon 30
Beech 43
Belleau 135
BENARY Contugated aldehyde synthesB 31
Benary 115
Bender 158
Ben Ishu 417-416
Benkeser 34
Benzldlne 437
Benzoin 225
Benzyllc =ctd 235
Bergmann 109
BERNTHSEN Acndine synthes=' J2
BIGINELLI Pynrnldone synthes$ 33
BIRCH- HUCKEL- BENKESER Reduction 34
BISCHLER Benzotrlazme synthe$s 35
BISCHLER - MOHLAU Indole synthess 35
BISCHLER - NAPIERALSKI Isoqumollne
synthes 36
Blame 312
BLANC Cychzatlon 36
BLUM Azmdme synthesis 38
BODROUX- CHICHIBABtN Aldehyde
synthesB 39
BOGER Heteronycle synthess 40
BOORD Enol ether synthess 41
BORCH Reductmn 42
Bormann 404
Boron 183
Borsche 123
BORSCHE - BEECH Aromatic aldehyde ynthesls

440 Names Index Namas Index 44 1
Bossat 272
BOUVEAULT Aldehyde synthesis 39
BOUVEAULT - BLANC Reduction 44
BOUVEAULT. HANSLEY - PRELOG - STOLL
Acyloln synthesis 44
BOUVEAULT - LOCQUIN Ammoactd
synthesis 45
BOYLAND - SIMS o-Hydrosyanlhne synthesis 46
von BRAUN Anne degradation 47
von Braun 324
Braverman 266
BREDERECK In'dazole synthesis 48
BROOK Sdakatone rearrangement 49
BROWN Stereo,=electlve reduction 50
BROWN Hydroboratlon 51-52
Brunner 104
BRUYLANTS Ammatmn 53
Bruylants 193
BUCHERER - LE PETIT Naphthol(naphthylarnme)
synthesis 54
BUCHNER - CURTIUS - SCHLOTTERBECK
Homologehon 55
B0ch 2S0
BURGESS Dehydration reagent 56
BURTON Tnfluoromethytatc, n reagent 57
Buttenberg 134
Caghotl 18
Campbell 172
CANNIZZARo OxldatlOn-reduchon 58
CARROLL Allylalc, n 59
Ca=to 363
CHAN Reducbon of acetylenes 6O
CHAPMAN Rearrangement 61
Chen 3g0
CHICHISABIN Arnlnahon 62
CHtCHISABIN Pyndme synthesis 83
Chlchibabln 39
Chodloewcz 147
CIAMtCIAN Photocouphng 64
CIAMICIAN * DENNSTEDT Cyclopropenatlon 64
Clalsen 3N
CLAISEN - GEUTER o DIECKMANN Ester
condensatmn 65
CLAISEN. IRELAND Reanngement 66
Clarke 111
CLAY o KINNEAR - PERREN Phoq)honyl chloride
=ynthesm 67
CLEMMENSEN Reductmn 88
CLOKE - WILSON Rearrangement 6g
Cohen 385
COLLMAN Carbonyklhon reagent 70
Colman 140
COMBES Qumohne synthesis 71
CONIA Cyclizatlon 72
COOPER. FINKBEINER Hydromagnesistc, n 73
COPE Rearrangement 74
COPE - MAMLOC - WOLFENSTEIN Olefin
synthesis 75
COREY Oxidizing reagents foў alcohol= 76
COREY Enantmelectiva bOrane reduobon 77
COREY Homologatwe epoxldetmn 78
COREY - KIM Oxchzmg reagent 79
COREY- WINTER Alkene synthesis 80
CORNFORTH Rearrangement 81
Crafts 131
CRIEGE Glycol oxidation 82
Cnatol 163
CURTIUS Rearrangement 83
Cua,u ss
DAKIN Oxidation 84
DAKIN • WEST Acylat|on 84
DANHEISER Annulatlon 85
DANISHEFSKY Sdyloxyclenes as
DARAPSKI Ammoacd synthesis 87
DARZENS- NENITZESCU Ac3datlon 87
DARZENS Epoxde symhesis 88
DAVIDSON Oxazola synthesis 89
DELEPINE Aldehyde oxidation 89
DAVIS Oxidizing reagent 9O
Decker 127
DELEPINE Amine symhesis 91
DE MAYO Cyoloaddtc, n g2
DEMJANOV Rearrangement 93
Denlges 219
Dennstedt 64
DESS o MARTIN Oxidizing reagent 94
Dieckrnann 65
DIELS - ALDER Cyclohexene synthesis 95
DIMROTH Rearrangement 
DJERASSI - RYLANDER Oxldatmn 97
Doebner 2O5
DOEBNER - MILLER Quinine m/nthesis 98
DOERING - LA FLAMME A/ne synthe=a 9
DONDONI Homologtlo 100
DO'rz Hydroqumone =/nthesis 101
Drechol 123
Draw=on 12
DUFF Aldehyde symhesis 102
DCrl-r. WORMALL Azde formaon 102
Duisberg 291
EHRLICH - SACHS Ak:lehyde synthesis 103
EINHORN - BFIUNNER Tnazole synthesis 104
E=tert 7
ELBS Condensation 105
ELBS Oxdanon 106
EMMEFIT Reductve condensation 107
Emmons 181
ENDERS Chlral reagent 108
Engel 166
Erdmann 4OO
ERLENMEYER - PLOCHL- BERGMANN
Arrunoacld synthesis 109
ESCHENMOSER Fragmentation 110
Eechenmoeer 241
ESCHWEILER - CLARKE Amine methylatmn 111
ETARD Oxdatmn 112
Evans 265
EVANS Ch=ral auxflmry 113
FAWORSKI - WALLACH Rearrangement 114
FEIST* BENARY Furan synthesis 115
Fedvacllan 394
FELKIN Cycltzat|on 116
Fenton 327
FERRARIO - AKE RMANN Thmcychzaton 117
FERRIER Carbohydrate synthesis 118
FERRIER Choral cyclohexanone synthesis 119
FINEGAN Tatrazole synthesis 120
Fmkbemer 73
RNKELSTEIN - GRYSZKIEWICZ -
TROCHIMOWSKI - McCOMBIE
Halide displacement 121
Ftr'th 183
Flecher lO, 203. 315
FISCHER Oxazole synthesis 122
FISCHER- BORSCHE - DRECHSEL Indole
synthesis 123
FISCHER- HEPP Nltrosoernme rearrangement
124
FLOOD Sllyl chlonde synthesis 124
FWTIG Ptnacolone rearrangement 125
FORSTER Dazo synthesis 126
FORSTER - DECKER Amine synthesis 127
Foulds 322
FRANCHIMOND Cyano succmў acid
synthesis 128
FREUND - GUSTAVSON Cyclopropane
syhesis 12g
FREUDENBERG - SCHONBERG Xanthate
rearranoemem 130
Fraytag 175
FRIEDEL - CRAFTS Alkylaton-acylaton 131
FRIEDLANDER Oulnolme synthesis 132
FRIES Phenol ester rearrangement 133
FRITSCH - BUTTENBERG - WtECHELL
Acetylene synthesis 134
Frltsch 303
FUJIMOTO - BELLEAU Cyclohexenone
synthesis 135
FUJIWARA Lanthamde (Yb) reaction 136
FUJIWARA Arytatlon, carboxylatlon 137
FUJIWARA o HECK Coupling 138
Fukuablma 329
Gabriel 323
GABRIEL Amine synthesis 139
GABRIEL- cOLMAN Renangement 140
G -,, 299
GAREGG - SAMUELSSON Olefmat|on 141
GASSMAN Oxlndole /nthesis 142
GASTALDI PyraZme symhesis 143
G attermann 332
GATTERMANN - KOCH Carbonylat=on 144
Geuter 65
GEWALD Heterocycle synthesis 145
GIRARD- SANDULESCU Reagent 146
GLASER - CHODKIEWCZ Acetylene coupkng
147
GOLD Reagent 148
Goldoerg 395
GOMBERG - BACHMANN - GRAEBE-
ULLMANN Arylaton 14,9
Graebe 149
GRIECO Reagent 150
GRIESS Deammatmn 151
Gnffith 234
GRIGNARD Reagent 152
Groshelntz 315
G ryszleww, z 121
GUARESKY-THQRPE Pyndonesynthe 153
Guatte 154
G ustavson 129
GUY- LEMAIRE - GuET'I'E Phenol
chlonnatlon 154
Haack 39g
HADDADIN - ISSIDORIDES (Beirut raactmn)
Qunoxakne synthesis 155
HALLER- BAUER Ketone clesvage 156
Hanldod 427
Hansley 44
HANTSCH Pyndne /nthesis 157
HASS- BENDER Carbonyl synthesis 158
HASSNER Azv:e azlndme synthesis 159

442 Names Index Names Index -43
Hessnsr 361
HASSNER - RUBOTTOM alpha
hydroxyl=ion 160
HAUSER BEAK Ortho hthlatlon 161
Hauser 354
HAYASY Rearrangement 162
Heathcock 171,433
Hack 138
HELL-VOLHARDT ZELINSKI Bronnatlon 163
HENBEST Indium reagent 164
HENRY Nitro condensation 165
Hepp 124
HERBST o ENGEL KNOOP - QESTERLING
Arnoacld synthess 166
HERZ Benzothlazola synthesis 167
Hlclonbottom 176
HILBERT JOHNSON Nucleolde synthesis 168
Hlilman 28
HINSBERG Thlophene synthess 168
HINSBERG STOLLI Indole, indoxyl
symhesm 169
HIYAMA Amnoacrylat a synthesm 170
HIYAMA - HEATHCOCK Steraosalectlve aliylaton
171
HOCH" CAMPBELLAzlrld'me synthesis 172
Hoesch 182
HOFMANN Arnde degradation 173
HOFMANN Isonltdle synthesis 173
HOFMANN Elimination 174
HOFMANN LOEFFLER - FREYTAG Pyrrokdlne
synthess 175
HOFMANN - MARTIUS REILLY -
HICKINBOTTOM Rearrangement
t7S
HOFFM - YAMAMOTO Stereosalectwe
allylaton 177
HOt.LEMAN Pmacol synthesis 178
HONZL-RUDINGER Peptlde synthesis 179
HORNER - KNOWLES - KAGAN Asymmetric
hydrogenation 180
HORNER WADSWORTH - EMMONS
Oleflnation 181
HOUBEN- HOESCH phenol acylation 162
Hulng Minion 426
Hubell 232, 29
H0ckel 34
HUNSDIECKER - BORODIN - CRISTOL - FIRTH
Decadooxylation-brornmatlon 183
Imamoto
IMAMOTo Cenum alk'ylatlon 184
Iretlnd 6s
ISAY Ptendme synthesis 18.5
lesldorldes 155
JACOBSEN Rearrangement 186
Janovsky 253
JAPP Oxazole synthess 187
JAPP KLINGEMANN Hyd'm.zone synthess 188
JAROUsSE MAKOSZA Phase transfer 189
JEGER Tstrahydrofuran synthess 190
JOHNSON Phenol allo/nylatlon 191
Johnson 168,197, 240
JONES Oxidation reagent 192
JULIA BRUYLANTS Cyclopropyt cart.nol
rearrangement 193
JUNG- OLAH VORONKOV Etheroleavage 194
KABE Chmmanone synthesis 195
Kagan 180
KAGAN MOLANDER Samanumreagent 196
KAISER JOHNSON - MIDDLETON Dlnltnte
cydlzatlon 197
KAKIS Rearrangement 198
KALUZA Isothlocyanate synlhesls 199
KAMETANI An',rle oxidation 199
KEINAN Sdane reagent 2OO
Kellogg 25
Kendall 246
KHAND PAUSON Cyclopentenone annulation
201
KHARASH - SOSNOVSKY Nlyllc oxidation 202
KILIANI FISCHER Sugar homologation 203
Kim 79
Kinnear 67
Kmler 416
KISHNER Cyclopropane synthesis 204
Kshner 426
Klmgarnann 188
KNOEVENAGEL DOEBNER. STOBBE
Condensation 205
Knoop 166
KNORR Pyrazole syntheas 206
KNORR Qulnollne synthesis 206
Knott 209, 284
Know, as 180
KNUNYANTS Fluoroldlo/tation 2O7
Koch 144
KOCHI Cross couphng 208
KOENIGS - KNORR Glycosldaton 209
KOHLER Isoxazole-N-oxlde synthesis 210
KOLBE Electrolysis 211
KOLBE SCHMIDT Sallcykc acid synthesis 212
KONAKA Oxidizing reagent 213
KONIG Benzoxazlns synthes,s 214
KORNBLUM Aldehyde synthes|s 215
KOSER Tosylatlon 216
Kostanoclo 321
KRIEF REICH Oleflnaton 217
Knewdz 306
KROHNKE ORTOLEVA Pyr|dlmUm salts 218
KUCHEROV DENIGES Hydratmn 219
KUHN WlNTERSTEIN Olefinatlon 220
Kuchtln 247
KUMADA FLEMING StereoseleCtlVe
hydroxylaton 221
KUMADA NEGISHI Cross coupling 222
KURSANOV PARNES Ionў hydrogenation 223
LADENBURG Pynd=ne benzylat=on 224
La Flame 99
LAPWORTH (Benzoin) condensation 225
Leszlo 255
LAWESSON Thlocarbonyston 226
LEBEDEV Methoxymelhylatlon 227
LEHMSTED TANASESCU Acndone synthess
228
LEHN Cryptand synthesis 229 230
Lema,ra
Lemeux
Le Petit 54
LEUCKARDT Thiophenol synthess 231
LEUCKARDT - PICTET HUBERT
Phenanthndme synthess 232
LEUCKARDT WALLACH Reductlve
arnmaton 233
Letras ,ў11
LEY GRIFFITH Oxidation reagent 234
I,JEBEN Hypohakde olodatlon 235
LIEBIG Benz./kc acid raan'angernent 235
Loeffier 175
LOSSEN Rearrangement 236
MACDONALD Porphynne symhess 237
MADELUNG Indole synthess 238
MAKOSZA Vloanous nudeophlllc
sub=t,tut,o 239
Makoaza 189
MALAPRADE LEMIEUX JOHNSON
Olaf m(diol)claavage 24O
Mamloc 75
MANNICH ESCHENMOSER Methylenation
reagent 241
MARKOVNIKOV Reg.electwlty 242
MARSCHALCK Arometў alkytaton 2
MARTIN Dehydratlng regent 244
Mamn 94
Maalus 176
MASCARELLI Fluorene synthesis 245
MA'i'OX KENDALL Dehydrohalogenatlon ,46
McComble 26 121
McCORMACK KUCHTIN RAMIREZPhosphole
synthess 247
McFADYEN STEVENS Ester reduction 24
McMURRY Coupling 249
Meerwem 4O3
MEERWEIN AIk3'latlon reagent 250
MEERWEIN PONNDORF-VERLEY
Reduction 251
MEISENHEIMER N-Oxide rearrangement 22
MEISENHEtMER - JANOVSKY Complaxes 253
MELDRUM'S Amd 254
MENCKE LASZLO Nitration ol phenols 2.55
MENZER Benzopyran syntheSl 256
MERRIFIELD PeptKe synthess 257
MEYERS Asyrnmetrў symhess 256
MEYER - SCHUSTER Propargyl alcohol
rearrangement 259
MICHAEL Adddlon 26o
MtCHAELIS BECKER - NYLEN Phosphonlator
261
Mchaels 5
Mlddleton 197 352
MIESCHER Degradation 262
MILAS Olafm hydroxylation 263
Mi#er 98
MILLER - SNYDER Alyl wan=de synlhesls 264
MINISCI Aromatm an'nation 265
MISLOW BRAVERMAN - EVANS
Rearrangement 266
MITSUNOBU Displacement 267
Moffatt 298
Molander
M0I=,. 3S
Mosar 411
MUKAIYAMA Stereoselectlve aldol
condensation
MOiler 303, 355
MURAHASHI Allylў alkytion 269
Nametlon 4O3
NAZAROV Cyclopentenone wntheas 270
Napiorablo 36
NEBER Rearrangement 271
NEBER - BoSSET Oxmdola or
sy.them 272
NEF Reaction 273

444 Names Index Names Index 445
Negishl 222
NENITZESCU Indole synthesis 274
Nenltzescu 87
NIEMENTOWSKI QulnaZolons synthesis 275
NOYORI Chlral homogeneous hydrogenation
276 277
Nylon 261
O°DONNELL Amlnoacld synthesis 275
Oesterllng 166
Olah 194
OLEKSYSZYN Annophosphonlc acld synthesis
278
OLOFSON Reagent 279
OPPENAUER Oxldat=on 280
OPPOLZER Chffal reagent 281
Ortolava 218
ORTON Haloanlhne rearrangement 282
OSTROMISLENSKY Butadlens synthaais 282
OVERMAN Pyrrohdme synthesis 263
PAAL KNORR Pyrrola synthesis 284
PADWA Annulatlon 285
PAQUET'I'E Olahnahon 286
PARHAM Cychc ether synthesis 287
PARNES Gemmal drnethylation 288
Pames 223
PASSERINI Condensation 289
PATERNO BUCHI 2+2 Cycloaddltlon 290
PAYNE Rearrangement 290
Pauson 201
von PECHMANN Dlazo olefln cycloaddltlon 291
von PECHMANN DUISBERG Coumann
synthesis 291
PEDERSEN Crown ethers 292
PERKIN CarboxdlC acid(ester) synthesis 293
PERKIN Coumann rearrangement 293
PERKoW Vinyl phosphate synthes,,= 294
Perren 67
PETERSON Olefination 295
PFAU - PLATTNER Cyclopropane synthesll 296
PRTZINGER Qumohne synthem 297
Pfannlnger 360
PFITZNER MOFFATT Oxidation 298
Pfannenatisl 357
Pcat 232
PICTET - HUBERT - GAMS Isoqulnoline
synthesis 299
PICTET - SPENGLER Isoquioollns synthesis 299
PILLOW- ROBINSON Indole synthelis 300
PINNER Imlno ethers synthesis 300
Pacol 17
PIRKLE Resolution 301
Plattnar 296
PI6chl 109
POLONOVSKY N Oxide rearrangement 302
POMERANZ FRITSCH SCHLITTER MULLER
Isoqulnohne synthesis 303
Ponndod 251
POSNER Tnoxane synthesis 3O4
Prelog 44
PREVOST WOODWARD Olefln
hydroxylation 305
Prey 433
PRINS KRIEWlTZ Hydroxymethylatlon 306
PSCHORR Arylatlon 307
PUMMERER Sulloxlde rearrangement 308
Quellat 37
RAMBERG BACKLUND Olehn synthesis 309
RamlraZ 247
RAPP STOERMER Benzoluran synthesis 310
REETZTItamum alkylatlon 311
REFORMATSKY BLAISE Zinc alkylatlon 312
Regles electlvlty 242
REGITZ DlaZo transfer 313
Reich 217
Redly 176
REIMER TIEMANN Phenolformylatlon 314
REISSERT- GROSHEINTZ FISCHER
Cyanoamme reaction 315
REPPE Acetylene reaction 316
yon RICHTER Aromatic ўarboxylatlon 317
yon RICHTER- WIDMAN - STOERMER
Cinnohns synthesis 318
RILEY Selenium dioxide oxidation 319
Rlmml 4
RITTER Amda.on 320
Robinson 3O0
ROBINSON Annulsbon 321
ROBINSON - ALLAN - KOSTANECKI Chromone
synthesis 321
ROBINSON - FOULDS Qulnohne tnthalls 322
ROBINSON - GABRIEL Oxazole synthes,,= 323
ROELEN Carbonylation 323
ROSENMUND - yon BRAUN Aromatio cyanation
324
ROSENMUND Araonyatlon 324
ROSENMUND - SAITZEW Reduction to
aldehydes 325
ROTHEMUND Porphme synthesis 329
ROZEN Hypofluonte rlagents 3
Rozen 352
Rubottom 160
Rudlnger 179
RUFF FENTON Degrade.on 327
RUPE Rearrangement 328
RUZICKA FUKUSHIMA Rearrangemanl 329
Ryander 97
Sachs 103
Ssitzew 325
SAKURAI Allylatlon 330
Samuelsson 141
SANDMEYER Isattn synthesis 331
SANDMEYER GATTERMANN Aromat-
substitution 332
SanduleScu 146
SARETT Oxldclng reagent 333
Scheller 21
SCHIEMANN Fluorination 21
Schllttar 303
Schlotterbeck 55
Schmldt 212
SCHMIDT Rearrangement 334
SCHMITZ Dmzmdme synthesis 335
SCHOLL Polyarometio synthesis 336
Scholl lS
SCHOLLKOPF Arnlnoacld synthesis 337
SCHOLTZ Indohzlna synthesis 338
Schinberg 130
SchOol 379
Sch&nlg 427
Schroatar 342
Schuster 259
SCHWARTZ Hydrozlroonation 339
SCHWEIZER Allylamlns synthesis 340
SCHWEIZER Rearrangement 341
Semio 434
sEMMLER - WOLFF - SCHROETER Ox.'ne
arornatzatmn 342
SIMONIS Banzopyrone synthesis 342
Shq-o 16
SHARPLESS Asymmatnc epoxldatlon 343
SHARPLESS Asymmatnc dydroxylation 344
SHERADSKY Rearrlmgernsnt 345
SHESTAKOV Hydrane symhesis 346
SIEGRIST Stlbens synthesis 347
SIMMONS - SMITH Cyclopropana synthesis 349
S=rm 49
Sml 366
SKATTEBL Rearrangement 349
SKRAUP Oumolme synthesis 35O
SMILES Aromatic rearrangement 351
SMITH - MIDDLETON - ROZEN Ruonnatlon 352
Smith 348
Snyder 264
SOMMELET Aldehyde synthesis 353
SOMMELET HAUSER Ammonlumyhd
rearrangement 354
SONN MULLER Aldehyde synthesis 355
Snsnovsky 2O2
SOULA Phase transfer catalyst 356
SPENGLER PFANNENSTIEL Oxclation 357
Spongier 299
STAAB Reagent 358
STAUDINGER Azlde reductmn 359
STAUDINGER PFENNINGER Tharans dlomde
synthesis 360
STEGLICH HASSNER DireCt esterlhcatlon 361
STEPHEN Aldehyde synthesis 362
STEPHENS CASTRO Acetyans cyclophans
synthesis 363
STETTER 1,4 Dlcarbonyl synthesis 364
Stevens 18 248
STIEGLITZ Rearrangement 36,5
STILES SISTI Formylation 366
STILLE Cross coupkng 397
STILLE Cerbonyiatlon 368
Stob 209
Stoerrner 310, 318
Sto, 44
St oll 169
STORK Ensrmne alkylation 369
STORK Cyanohydnn alkylatron 370
STORK Radical cyclRation 371
STORK Raductlve cydtzatmn 372
STORY Macrocyclio synthesis 373
STRECKER Ammoacld synthesis 374
sTRYKER Ragloselectve reduction 375
Suhl 435
SUZUKI Viny coupling 378
SWARTS Halogen exchange 377
SWERN Omdaton 379
SZARVASY - CHOPF Cerbomethox3datlOn 37
Tanesescu 228
TEBBE olehnstion 390
TEER MEER Dlmtroalkans synthesis 381
TEUBER Qumone synthesis 382
THILE - WINTER Oumone catoxyUon 383
TIEMANN Reln'angement 383
Tiemenn 314
TIFFENEAU Ammcmlchohol rearrlngament 384
TISCHENKO - CLAISEN Aldehyde to liter
conversion 34

446 Names Index
TIPSON COHEN Oleflnatlon 385
Todd 8
TRAHANOVSKY Oxidation 386
TRAUBE Purlne synthesis 387
TREIBS Allyў oxidation 388
Trochlmowskl 121
TROST Cyclopentanatmn 389
Trost 392
TROST CHEN Decarbox3datlon 390
TSCHUGAEFF Olefin synthesis 391
TSUJI - TROST Allylatlon 392
Tsup 402
UGI Condensation 393
UIImann 149
ULLMANN FEDVADJAN Acndlne synthesis 394
ULLMANN - GOLDBERG Aromatў
subsntutlons 395
VAN BOOM Phosphorylatlng reagent 396
Van Do m 6
VAN LEUSEN Reagent 397
VEDEJS Hydroxylatlon 398
Venketaraman 14
Verlsy 251
V'dllger 13
Viehe 399
VILSMEIER - HAACK - VIEHE Reagent 399
VOIGHT Alpha-ammoketone syntheem 400
VOLHARDT - ERDMANN Thlophene
synthesis 4O0
Volhardt 163
VORBRUGGEN Nucleoslde synthesis 401
Voronkov 194
WACKER - TSUJI Olefln oxldahon 402
Wadsworth 181
WAGNER. MEERWEIN - NAMETKIN
Rearrangement 403
WALLACH Azoxybenzene rearrangement 403
Wallach 114. 233
WASSERMANN - BORMANN Macrocyclic lactam
synthesis 404
WEERMAN Degradation 405
WEIDENHAGEN Imidazole synthesis 406
WEINREB Ketone synthesis 407
WEISS Annutetlon 408
WENCKER AZlridlne synthesis 409
WENZL - IMAMOTO Reduct=on 410
WESSELY MOSER Rearrangement 411
WESTPHALEN LETREE Rearrangement 411
West 84
Weygand 424
WHARTON Ole|ln synthesis 412
WHITING Dlene synthesis 413
WlDEQUIST Cyclopropane synthesis 414
Wldman 318
Wlechell 134
Wmland 2O
WILKINSON Calbonylatlon dacarbonylatlon
catah/st 415
WlLLGERODT - KINDLER Rearrangement 416
WILLIAMS BEN ISHAI Ammoacld ynthesis
417 4e
WILLIAMSON Ethers synthesis 419
Wilson 69
Winter 80. 383
Wmtersteln 220
WlSSNER Hydroxy ketone synthesis 420
WITTIG Olefm synthesis 421
WITTIG Rearrangement 422
WOHL- AUE Phenazlne synthesis 423
WOHL- WEYGAND Aldose degradation 424
WOHL ZIEGLER Bromlnetlon 423
WOLFF Rearrangement 428
Wolff 342
WOLFF- KISHNER HUANG MINLON Reduction
42e
WOLFRAM SCHORNIG -HANSDORF
Carboxyrnet hylatlon 427
Wolfenetem 78
Wormall 102
WOODWARD Peptlde synthesis 428
Woodward 308
WURTZ Coupling 429
YAMADA Coupling reagent 430
YAMAGUCHI Lactontzatlon reagent 431
YAMAZAKI Cyanoanlllne synthesis 432
Yamamoto 177
ZEISEL. PREY Ether cleavage 433
Zehnskl 163
ZIEGLER Mecrocyclic synthesis 434
Zlegler 423. 438
ZINKE- SUHL Cyclohexadenone synthesis 436
ZINCKE - ZIEGLER Synthesis of callxerane 436
ZININ Benzidlne (semldlne) rearrangement 437
REAGENTS INDEX
Acetaldoxlme 43
Acetlc acid 14 104 123 231 278 342 43, 412
Acetic anhydnde 20 36 87 109 262 "ў.O 302
308 321.342.383 411 4"2 433
Acetyl hypofluorte 326
A D mix ((x and 13) 344
Aluminum amalgam I07
Alummum bromide 288
Alurnlnumchlonde 68 117 133,144 16q 182,
207 232 288 336 435
Alurnnum isopropoxlde 251,28O 384
AIurntnum oxide 69,165
(S) (R) 1 Amino 2(methoxymethyl)-pyrrohdme
SAMP RAMP 108
Anla 126. 300. 356 372 407 408 416. 424
Arnmonlum acetate 89 338
Arnmon=um carbonate t2
Arnmonlum formate 187
Ardlne hydrobronde 38
Arsenic acid 29. 350
AZoisobutyrontrde (AIBN) 23.27. 26. 371
Bnum hydroxide 387
Benzenesulfonyl chloride 248 383
Benzophenone 280
Benzoqulnone 404
Benzoylchlonde 16 318. 424
Benzyl chlonda 167
3-Benzyl-5o(2-hydmxyethyl)-4-methy t 3
thloazohne 364
Bis(dibenzyhdaneacetone)palladlum 361
(R) (S) Bis-(dlphenylphosphlne-1.1' blnaphthy
(BINAP) 276 277
Bis(imldaz ol- 1-yl)t h lone 81
2.4-Bis-(4-rnethoxyphenyl)-l.3 dlthla 2 4
dlphosphatene 2 4 disulfide
(Lawesson reagent) 226
Bis(tnfluoromethylbenzene
met hanolo )diphenyls ulf ur
(Marbn) 244
BIs(trlph enylph osphlne ) nlc kel dlchloide 116
Boronrnethyl sulfide 82
Boron trlflate 113
Boron trlfuonde/etherate 118,177 223, 383
Bromine aztda 159 242
Bronne cyanide 47
Bromoform g9
Bromine 9 41 163 198 327
N Bromosuccmlnda NBS 262. 417. 423
Butylborane 50
t Butyl hypochlonte 142
Butyl Ithlum 99.134 161.170.191. 238. 26t
266. 286 287. 295. 337. 407. 42.
421,422
Calcium sulfate 71
Carbon dioxide 212
Carbon dsulflda 199. 391
1.1 Carbonyl d,midazole (CDI) 388
(Ca rboxymet hyl)t nmet hylammonlum hydrazlde
(Girard reagent) 146
( Carbornet hoxysulfamoyl)t nethylarmnonlum
self 56
Cetecho[ borane 77
Cenum 184
Cenum ammonium nitrate 386
Cesium fluoride 354
Clalfene 255
Chlorenne 335
2-Chloro-8.6-benzo-1 3-dloxaph osph orln-.4-
one 3
Chloўo bis(5 2 4-ўyclopentadlene-l-yl)dimethy-
aluminum methylene anlum 380
Chloeobis(5-cyclopentadleny)hydmzlrconlum 339
Chloroform 314
Chlommdў acid 164
m-Chloroperbenzoў acid (MCPBA) 160
N-Chlorosuccmlmda NCS 7g. 175. 309
Chlorosulfonlc acid 120
Chrome II III chlonde 171
Chromyl chloride 112
Chromium trioxide 192. 282 333
Chromium trioxide dlmethytpyrrzola 76
Cobalt catalyst 323
Cobalt octacarbony 201
Copper 3O2 324, 395

448 Reagents Index
Copper acetale 490i Electrochemical 210
Copper brome I Ethyl amine 151
Copperchlonde 87 147.199 202 224 332 363 Ethyl chlomlormate 199
Copper cyanide 260 Ethyl magnesium bromide/radicle 6.170. 413
Copper iodide 26g Ethyl nltnte 45
Copper mtrats 255 N-Ethyl-5-phenyhsoxazohne-3 sulfonate 428
Copper sulfate 27 373
Crown ether 260. 27g 292 Formaldehyde 1.241
Cryptande 229 Folmaldoxlme
Formamlde 39 48
1.4-Dlazabmyclooctane DABCO 2e. 3SS Formic acid 111.123.125 233 328
DlaZoacetlў 55. 296
Dlazomethane 7. 55 360
Heat 1.29.33 40. 48. 59 63 72. 74. 75. 81.86.
Dlazonlum salts 188 95 96.105.120 t21.123 130 133.
4-Dlallo/lammopyndme 160 145.157.168 169.174.176 185.
Dlbenzo (18) crown-6 84 195. 206 214. 218. 236. 256 274.
Dlcartxmyl bs(tfc)henylphosphine)nmkef 390 275. 278. 282. 283. 291. 324 325.
Dw.hlorodlcyanoqumone (DDQ) 285 341 345. 391 394
Dlchloromethylene dlmethylammonlum chloride (2.3.4.5 6 6) or (2,3 4 4 5 6) Hsxachloro
(Viehe reagent) 399 ўyclohexa 2.4 oў (2,5)dene-l-one
Dichloromet hytphosphme 247 154
2"4-Dlchloro-3.5-dimtrobenzcate dirhoOklm 55 1.5-Hexadlene chlorcrhodlum 180
Dmyclohexy carbodhmlde DCC 298. 361 Hexamethyfdisllazane 90. 42O
Dmyclopentadlenyttltanlum chlonde 73 Hexarnethylenetetramme 91. tO2. 353
Dlethyl alumlmum chloride 281 Hydrazme 87. t39. 248. 412. 426
Dlethylammo sulfur tnfluortde (DAST) 352 Hydrobromic acid 193 197
Dlethyf azodlcad)oxylate (DEAD) 267 Hydrochloocacid 3 66.122 124 144.300 307.
Dlethyl phosphlte 8 310 342 400. 407. 433. 437
Dlethyl phophoryl cyanide 430 Hydrofluoric acid 15 71.131
(+)Dlethyf tallrate 343 Hydrolodic add 332 411
Diiodosllone 200 Hydrogen 11.35. 45.166 356. 417
Dksopropy amine 59.170 Hydrogen peroxide 13 84. 263. 327. 373
Dlmethylammo-2 azaprop-2-ene-l-ylldene Hydroxytamlne 27. 417
dlmethylammontum chloride (Gold N Hydroxybenzenesullonamlde 4
reagent) 148 Hydroxy(tosyloxy)lodobenzene 151
4-Dlmethylammopyndine (DMAP) 361. 433 Hypophosphorcus acid 151
D,ett copper lithium 28O
Dlrnethyfformamlde DMF 211. 229
Direst hy(rnethylene)ammordum K>dide
Iide 26.141
Iodine 141. 218. 305
(Eschenmosar's salt) 241 Iodine azJde 159
Dlmethytpyrrazole chromium tdoxlde 76 Iodine fluoride 352
Dlmethyl sulfate 12 Iron chlodde 208 270. 433
Dlmethyl sulfide 7g Iron olbenzoylmethane Fe(dbm)2 20
DImethyl suffoxlde (DMSO) 78. 215. 296. 378 Iron oxle 427
Dimethyttitanlum dichloride 311 Iron sulfate 265. 327
3.S-C, nRrobenzenesulfony hydrzlde 110 Isoprene 434
1.3- Dlnltro-4-guombenzene 424
Dinttrophenylhydrazme (DNPH) 246 Lantanum ntcke alloy 410
DlphenyMiazomethane 25 Lead {11) acetate 109
D=phenylsllane 223
Lead (IV) tetraacetate 83.190 365
Dtpotassrnlron tetracad)onyl 70 Llthlm 31.34. 372
Reagents Index 449
Lthlumalun',num hydride (LAH) 18,172 Pentacyencamme feroate 27
286. 413 Phase transfer catalyst 173 189. 349 356
Lrlhlum cyanoborohydnde 42 Phenyk'nagneslum bromide 20. 39. 262
Lthlumd,sopropylamlde 66 370 (+. Plnene 51
Llthmm tnrnethoxyalunnlum hydnde .50 2(Phenylsullonyl) 3 phenyloxazlndme (Day=
reagent) g0
Phosphlmmlne 247, 269
Magnesium 19 gg, 152.366
Magnesium amalgam 178 Phosphlne tnphenyl 222 359
Manganese dioxide 425 phosphlte methyl s. 359
Methnesullonlc acid 30. 308, 409 Phosphorus red 163
Methanesuffonyl chloride 217 4O9 Phosphorus oxychloride 122. 232, 252, 299, 322
Methylrnagneslum brornldechkmde 135 172. phosphorus pentachlonde 30, 355
389. 413 Phosphorus perdoxide 36 252
Methoxymagnesum methyl carbonate 379 Phosphorus pentesuffide 402
Methoxymethyl methyl sullate 227 Phosphorus tatramdlde 2t7 220
N-Methylandlne 434 Phosphorus mchlonde 66
Methy{ hypofluonte 326 Pholochemlcal reaction 22 64, 92,175 183,
Methyl iodide 5 78,391,419 242, 290 425
Phthalazlne dlhydroqumme 344
Methyl kthlum 349
Mercury acetate 2O9, 221 Pipendme 153,205
Memury chloride 119 Platinum 204
Memury oxide 183 219 P|etmum oxide 166
Mercury mfluoroacatate 368 Polymer. chlorornethyleted 257
Morphokne 145. 369. 416 Polyphosphonc (PPA) 186. 236
Potassium arsere 324
Potass,Jm tert-butoxlde all 86. 99.166. 239. 309
1-(1-Naphthyl)ethyl lsocyanate 301
Nckel 45.116. 356. 374 Potassium carbonate 114 212, 275
Nickel Acaў 339 PotaSsium cyamde 203 2.5 315. 317 37O
Nickelcyanide 316 Potassium hydrmade 9 58 132.145. 204, 253.
Nickel peroxide 213 264. 293. 297 314, 342, 419. 423,
Nltrosyi chloride 22 432
p-Nltrosodlmethylandme 103 Potassium iodide 414
Nltroethane(methane) 10.158 potasslumSocyanete 346
Potassium nodsulonate (Fromy's st) 382
Osmmm tetroxide 240. 263 344 Potesslum permangenete 427
Ozone 108 Potass,Jm persulleto 46 106
Oxalic acid 203.4O5 Phthahrde 139
Oxazaborohdlne 77 Pressure 323. 393
Oxazoles (ch=ral) 258 Pyrne 224. 310. 333 436
Oxazolidone 113 Pyndmechlorochromate 76
Ozo dlperoxy mollbdenum(pyndme)hexamethyl- Pyridme p.toluenesUlonate (pPT. Gneco
phosphonctrlarre (MoOPH) 398 reagent) 150
Palldlum/BaSO 4 325 Reney Nickel 42
Palladium/Cad)on 6.35. 417 Rhodium 179
PalllKIii.ml acetate 2 137,138 389. 402 Ruthenlumtetroxde 20. 97
paltednJm chlonde 222" 402
Sallcyl chlomphosphlta 396
Palladlum(a) 392
Pemcetlc acid 13, 252 Semanum 184,196
Perchloric acid 12, 217 Selenium (oXlde 319
Pentacarbonyl/rnethoxy(phenyl)ўarbene/ Silver benzoate 305
chromium (O) Dz. reagent 101 Silver oxide 89,174, 254

450 Reagents Index
Slk'e lts 20
Sodium 34,44.115 129,429,434
Sodamldo 62.158. 260
Sodium acetate 14 104. 321. 403
Sodium arsende 21
Sodium azlde 63.189.179. 334
Sodium bis(2-methoxyethoxy)aJun.mum hydndo
SMEAH 60
Sodium borohydnde 2
Sodium carbonate 264
Sodium Cyarde t28. 374
Sodium cyanoborohyddde 42.127. 404
Sodium cthion 243
Sodium ethyte 61
Sodium hydrogen carbonate 299. 408. 428
Sodium hyddde 65.181. 205. 271. 351. 369
Sodium perauffato 143
Sodium hyxldo 12. 58. 84. 96.135. 235. 239.
273. 290. 292, 329. 393° 436
Sodium hypochlodle 126.173. 238. 348. 405
Sodium Jocle 385
So,urn meoxe 18. 85. 66.114.140.158.
206. 210. 238. 253. 271.285. 293.
365. 387
Sodlum nRdte 21.27. 63. 87. 93. I2.149. 228.
• . 24S. 3O7. 318. 332, 381. 384. 387
ooomm pedodata 20. 97. 240
Sodium tdacetoxyborohydnde 42.128
SUbum ematmale 377
117. 416
Sulfur tetraole 352
Sulfudc acid 11.13.15.17.125.162.186.187.
206. 228. 259. 291. 306. 320. 321.
323.331.342.350.403.409
Tetmbm fluonde 100.191
Tetmfluombodў acid 25O
TetmkJs(tdphenylphosline)palladium (O) 387.
368. 378. 392
Tetthyleneo'tamlne TMEDA 52
Totmm TMS 288
Terrnotum Penuthenate 234
Thlaum hydmxJdo 376. 419
"r)hydroxamlc 8cd 24
Tin chlonde (11) 268. 272. 362
Tin chlondo (IV) 232. 270. 336
Tin hydroxide (11) 151
Titanium alkoxlde 343
Titanium doxlde 282
Tltamum tetrachlone 37 73 85. 279. 316. 330
p-ToluenesulfonJc acid 122. 300
pToluenesulfony azKo 313
pToluenesulfoname 102
pToluenesulfony! chlonde 292
pToluenesulfonyl hydrzlde 11o
p Toluenesulfonyl methyflsocyanale(TosMiC) 397
Tnbu phosphlne 340
Tn'bu stannane 23. 26 371
2 4.6-Trichlorobenzoy c 431
Tdethymlr 155. 389
Trthy burate 312
Tey phosphlte 294
Tnett sdane 223. 418
TnfluoroacatJc acid 137. 223. 289
TdfluroacatJc ardlyddde 308. 378
Tdfluoromethycadmlum chk>nde 57
Tmethyl IOSphita 294
Tdmethysi lodge 194
Tnmethysi hydrotnoxe 304
Tnmoth4sflthlolm 10o
Tdmethytyf tdflate 401
TephenyPhcophlne 25, 38,138,141,421
Tdphenyasphr copper hyddae 375
1,1,1-Trt(acatyloxy). 1,1-dihydro-l,2-
4b°l°dox'3( 1G)one(Penodinane)
Tds(tnphonylphcophtne) chlorodnodlum 415
Uraa 245
Wnyf chkroormate 279
Xamhates 231
Yterbtum 136
Zinc 41.87, lo5,129 231,249, 312. 385
ZJc amalgem 68
ZJc copper couple 343, 388
Zinc chlodde 32, 37, 41, 98,131,167,1760182,
193
REACTIONS INDEX
Acylatlon 84. 87 131.182,383
Adddton 136 152 216.219.260 300 316 364
Adddlonstereoselectlve 81. 267 311
Addttton regoselectlve 51. 242
Aldolizatlon 168.170. 208
Aldokzaton enantloselectwe 113
AJJone synthesis 99
Alkylatlon 5.11.18.19.28.131.184. 207. 243.
289.312. 369
Nk'ylatlOn on oxygen 250
Alkylabon gemmal 297
Alklatlon on N (mono) 127
Nk'yiatlon ortho 161
AUylabon 202. 269. 389. 392
AlabOn stefeoseloctlve 171.1T/. 330. 340
Al'ynylaon 191
Amldaton 32O
Ammaton 53. 54. 62. g2.127.139. 232. 268
Amioo =clde. peptK|es 45. 87.168 179. 287. 275.
374. 393. 417. 428. 43O
Amino methylation 11 I. 241
Annulatlon 19. 201. 248. 27O. 285 321. 342. 350.
363. 389. 394. 4O2, 423
Annubon regocomrolled 85
Arommtzstlon 105, 342
Arsonylatlon 21.29. 324
A/lllion 13.15. Ig. 137.149. 307
Asymmetrў synthesis 108. 258. 337. 417
AZldbon 102.159
Azlndme synhess 36,172, 408
Calomrene syntheses 436
Carbomethoxylation 37g
CadoonystlOn 2, 43, 70,144,158, 323, 418
Cadooxylstlon 137. 212, 317
Cmboxymethylatlon 427
Ch,'al reagent 261
Cleavage 16.97.150.186.194. 240. 433
Condensabon 31.6O. 128. 218. 224. 228. 228.
254. 282. 289. 347. 36O. 4OO. 401
Convermon 273. 42O
CoupSng 64.138.147. 2O8. 249. 367. 429. 43O
Coupllng *tereospecў 222
Crown ethers 292
CPptands 229-230
Cyanat,on 264. 315. 324. 397. 435
CycSzatlon 10.11.12.14.17. 32. 33. 35. 36.44.
48. 63. 71.72. 69. 98.104.105.115.
117.122.123.129.132.135.142.
143.145.153.155.167.167.16.
169.187.195.196.197.206.210.
214. 228. 232. 236. 256. 272. 274.
275. 284. 291. 93.297. 299. 300.
303. 310. 318, 321,322. 323. 331,
335. 336. 339. 371. 372. 387. 397.
CycSzation regoselcve 101
CyckzatJon stereoselectwo 116
Cycloaddelon 92.120. 290. 291
Cyclocondensatlo 185. 274. 267. 325. 423
Cyclopropanatton 84. 204. 296. 341. 414
Detlkylatlon 279
Dearnabon 23.181
Decarbonyiatlon 415
Decadooxylation 24, 21 I, 390
Degridatlon 20. 47. 83.173. 262. 327. 34e,
4O5. 424
Dehalogonetion 246. 412
Dehydration 56
DehydrohalogenlllOn 246
Daoxygenation 26
Dlalkylamme methytion 146
Dlazo reoctlon 126. 313
Deno symhes8 40. 95. 413
Drone synthesis rog'ontrollod 66
Drone synthesis stereocontroHod 86. 281
Dtmonzation 178
DlspaCernent 121. 267
Eiectrochernlsln/ 211
EIImmatton 75.174. 391
Eno reaction 1. 281
Epoxatlon 78. 88. 244
EpoxJdahon choral 343
Estsrlfўaton 358. 381. 384

452 Reactions Index
Fluonnaton 21,207, 326. 362
Formylahon 39,102 103, 218, 314, 353,
366 399
Fragmenteton 3O. 110
Free radical reaction 178,190,196
Functlonallzatlon 22
Glycosdatlon 209
Hmloelkylatlon 37
Halogenatlon 154,163 423
Helogenatlon regoselactve 164,160
Homologetlon 7, 56, 78,100, 203
Hydrazone synthem 188
Hydroboraton 61 52
Hydrogenahon esyrnmetnc 180. 276-277
Hydrogenat,n Ionic 223
Hydrolysis 200
Hydromagnesat,n 73
Hydroxylaton 160 221. 263. 305. 344. 388
Hydroxymethylatlon 306
Hydrozrconatlon 338
Lactam macrocyc[ic 404
Lactonzzahon 431
Methoxymethylatlon 227
Mulhstep reactions 6, 41,109, 229, 262, 408,
407, 417, 420
Naratlon 288. 381
Nltrosetlon 27
Nucleoslde synthess 183. 401
Olefinahon 18 28. co, 141 181, 217. 220, 244,
26, 295, 360,'388 391. 412. 421
Oxldabon 4, 46.76, 79, 82. 84.'89, 90, 94, 97,
106,112,192,199. 202. 213. 234,
235,244 260. 298, 319, 333, 357,
378, 382, 384, 386, 366, 4o2
Phase transfer catelysl 189. 386
Phosphonetlon 67, 247. 278, 294
Phospholatlon S, 261,396
Rearrangement 3,17 30, 4.9. 69, 61.66, 69, 74,
81.83 93, 96,114,118,124,126
130.133 134,140,162.176,186,
193.198 235, 236, 252. 259, 266,
271,282, 290, 293. 3o2, 308, 326,
329. 334, 341,346, 349, 351,354,
385, 383,384, 403, 411,416, 422,
425, 437
Rearmngernent mgmatroplc 1,266, 427
Redox reatlon 58
Reductlon 34 44. 68.136,196, 248, 261,325,
365, 358, 359, 362, 372. 407, 410.
426
Reduction ermntloselectve 77
Reduction regloselacl,/e 376
Reducon selective 42,164
Reductlon atereosectwe 50
Reduction stereospeczhc 6O
Reductwe arnmatlOn 42. 233
Reductwe coupling 107
Rductve mdnaton 200
Ring enlargement 9.13.114. 365. 384. 404
Rzngcontractlon 114. 426
Resolut,n 301
Substdutlon 136,152,163, 231. 239, 332,
377, 395
Thllarbonyltlon 226
Tnfluorornthylatlon 
Vinyl COUlmg 376
Miscellaneous reactlons 124,148,161,173,199,
300, 316, 435

FUNCTIONAL GROUP TRANSFORMATIONS INDEX
 126 313 to3 112 319, 399 01, 319 415 15,137
148 23, 31. 33 385
 A 1. 7 , . , , 74 1 1  , 242  5 73   101 7 1 247 21 2   2, 87,1 219 73 9 2 
,   116, 7,   259 6 9 , , 
,, 0, 9, 376  , 3, 
I, 9,  372
373, 3, 410
 13  , ,  2 1 1,  149. , 7,  . ,  27  5 161  1, 314  1 7, 4, 7
,, ,1,1,, ,9 41   377, 1 1 1  ,4 31. 70,, 13,
411, 413, 421 ' '  ,  ,
sc.   , 2
No, ., o, ,   
Cl 3  317,379, 11  1, , 423
 s 245 2  N,  1 6 3,  47 ,     , 142 , 9 , ,   7
111.,1, ,  m, sT,s,
4, 6. 249,    , , , 275
P,,ac =1 ,.3
5, 8, 21 49, 67, 7
 4 1   ,  24, , M, 1, 41 ,  6  , , 370 4,  , , w 374 lZ ,  ,  , 1 7,
 421  . i .
4, 4S, 4 , 2 , I  ,   247, e,   , m, I    I 374 ,  IS I, , I I 
,41Z421 ,,, 4,   ,, 7,,,3
414   3, 0, ,,  7 7,
, 179. 257, 5
, 3, 4, 4