Table Of ContentSynthesis of lactones and lactams
THE CHEMISTRY OF FUNCTIONAL GROUPS
A series qf ciclvcinced treotises under the generril editorship of'
Professor Siiiil Pcrtai
The chemistry of alkenes (2 volumes)
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The chemistry of alkenes (2 volumes)
The chemistry of carboxylic acids and esters
The chemistry of the carbon-nitrogen double bond
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Supplement A. The chemistry of double-bonded functional groups (2 volumes, 4 parts)
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Supplement C: The chemistry of triple-bonded functional groups (2 parts)
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UPDATES
The chemistry of a-haloketones, a-haloaldehydes and a-haloimines
Nitrones, nitronates and nitroxides
Crown ethers and analogs
Cyclopropane derived reactive intermediates
Synthesis of carboxylic acids, esters and their derivatives
The silicon-heteroatom bond
Synthesis of laclones and lactams
Palai's 1992 guide to the chemistry of functional groups-Saul Pafar
yc=o
I
Synthesis of lactones and lactams
b?,
MICHAEAL. OCLIARUSO
and
JAMES F. WOLFE
Virginia Polytechnic Institute and State University
Edited by
SAULP ATAaI nd ZVIR APPOPORT
The Hebrew University, Jerusalem
Updates from the Chemistry of Functional Groups
1993
JOHN WILEY & SONS
CHICHESTER * NEW YORK * BRISBANE * TORONTO SINGAPORE
An Interscience@ Publication
Copyright 0 1993 by John Wiley & Sons Ltd,
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All rights reserved
No part of this book may be reproduced by any means,
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Library of Congress CatalOginK-in-P UbliCalion Data
Ogliaruso, Michael A.
Synthesis of lactones and lactams / by Michael A. Ogliaruso and
James F. 'A'olfe ; edited by Saul Patai and Zvi Rappoport.
p. cm.-(Updates from the Chemistry of functional groups)
'An Interscience publication.'
Includes bibliographical references and indexes.
ISBN 0 471 93734 7
I. Lactones-Synthesis, 2. Lactams-Synthcsis. I. Wolfe, James
F. 11. Patai, Saul. 111. Rappoport, Zvi. 1V. Title. V. Series.
QD305.AZ033 1993 92-2893 2
547'.637-d~20 CI P
British Library Cataloguing in Publication Data
A catalogue record for this book is available from the British Library
ISBN 0 471 93734 7
Typeset by Thomson Press (India) Ltd, New Delhi, India
Printed and bound in Great Britain by Biddles Ltd, Guildford, Surrey
List of contributors
M. A. Ogliaruso Department of Chemistry, College of Arts and Sciences,
Virginia Polytechnic Jnstitute and State University,
Blacksburg, Virginia 24061 -01 22, USA
J. F. Wolfe Department of Chemistry, College of Arts and Sciences,
Virginia Polytechnic Institute and State University,
Blacksburg, Virginia 24061-01 22, USA
V
Foreword
This new volume contains the original chapter on ‘The synthesis of lactones and lactams’
by Professors J. F. Wolfe and M. A. Ogliaruso, which appeared in 1979 in Supplement
B: The chemistry of acid deriuatiues. To this original chapter, the same two authors have
added an appendix of about three times the size, albeit the period discussed in the
appendix is less than ten years. This situation is similar in the Update volume on the
Synthesis of carboxylic acids, esters and their derivatives, also by the same two authors.
We would be very grateful to our readers if they would bring to our attention omissions
or mistakes in this or in any of the other volumes of the series.
Jerusalem SAULP ATAI
July 1992 Zvr RAPPOPORT
vii
Preface
Because of the importance of lactones and especially lactams as starting materials for
the preparation of a large range of antibacterial agents, methods of synthesis and inter-
conversions of these functional groups are of great significance to a large group of
practicing organic chemists. Because of this, and in order to provide the series, The
Chemistry of Functional Groups, with a single source of information on general methods
for the synthesis of lactones and lactams, a chapter on the synthesis of lactones and
lactams was authored and appeared in Supplement B: The Chemistry of Acid
Deriuafiues, Chapter 19, pp. 1063-1330. That chapter contained descriptions of the most
common methods for the synthesis of lactones and lactams, with emphasis on preparative
techniques that appeared in the primary literature during the period 1967 through 1976.
The present monograph volume on the synthesis of lactones and lactams is our
response to an invitation from the Editors and publishers of the 'Functional Groups'
series of books to combine the material contained in the original chapter with new
methodology from the literature for the period 1976 to the present. The format for this
combination consists of the original text as published in 1979, along with an up-to-date
Appendix containing the newer material in the same format as used earlier.
This monograph is designed for the practicing chemist who seeks a convenient, single
source for synthetic methods leading to lactones and lactams. An attempt has been made
to include sufficient detail and examples of typical preparations to allow the reader to
make a rational choice from among several alternative methods. Obviously there will
be synthetic procedures that have not been included or that have been given only cursory
attention, but it is sincerely hoped that what has been included will be of help and
interest to our colleagues in the international organic chemistry community.
Deep gratitude is expressed to the Department of Chemistry at Virginia Polytechnic
Institute, while sincere appreciation Is extended to Marion Bradley Via, without whose
generosity this project would not have been possible.
Blacksburg, MICHAEL A. OCLIARUSO
Virginia JAMES F. WOLFE
1992
ix
Contents
1. The synthesis of lactones and lactams . . . . . . . . . . . . . . . . . . . . 1
2. Appendix to 'The synthesis of lactones and lactarns' . . . . . . . . . . . 269
Author index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1029
Subject index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1065
xi
Abbreviations
The following abbreviations, arranged alphabetically below, are used consistently
throughout this volume
Ac acetyl DMAP 4-(N,N-dimethylamino)-
acac acet ylacetonate pyridine
AIBN azobisisobutyronitrile DME 1,2-dimethoxyethane
An anisyl DMF N,N-dimeth ylformamide
anhy. anhydrous DMSO dimethyl sulphoxide
Ar argon, aryl 2,4-DNPH 2,4-dinitrophenyl hydrazine
atm atmospheres DPPA diphenylphosphoryl azide
BiPY b i p y r i d y 1 dPPb 1,4-bis(diphenylphosphino)-
Bn benzyl butane
BOC t-butoxycarbonyl EDTA ethylenediaminetetraacetic
BSA bis( trimethylsilyl)acetamide acid
Bu butyl EEDQ 2-ethoxy- l-ethoxycarbonyl-
Bz benzo yl 1,2-dihydroquinoline
C cyclo e.e. enantiomeric excess
CAN ceric ammonium nitrate Et ethyl
CP q5-cyclopentadienyl eV electron volts
CSI N-chlorosulphon yl Fc ferrocene
isocyanate fod tris(6,6,7,7,8,8,8)heptafluoro-
CTAB cetyltrimethylammonium 2,2-dimethyl-3,5-
bromide octanedionate
DBN Fu fury1
1,5-diazabicyclo[4.3.O]non-
5-ene dyme ethylene glycol dimethyl
DBU ether
1,8-diazabicyclo[5.4.0]-
undec-7-ene h hours
DCCD N,N’-dicyclohexyl- Hex hexyl
carbodiimide HMPA hexamethylphosphortri-
DCE 1,2-dichloroethane amide
DDQ 2,3-dichloro-5,6-dicyano- hv irradiation with light
1,4-benzoquinone HOMO highest occupied molecular
DEAD diethyl azodicarboxylate orbital
DIAD diisopropyl azodicarboxy- I is0
late IPNS isopenicillin N synthase
DIBAL di(t-buty1)aluminium IR infrared
DICD diisopropylcarbodiimide kbar kilobar
diglyme diethylene glycol dimethyl LAH lithium aluminium
ether hydride
...
XLll
xiv Abbreviations
LCAO linear combination ofatomic R any alkyl group
orbitals r.t. room temperature
LDA lithium diisopropylamide Rx reaction
LTEA lithium triethoxyaluminium S secondary
hydride (salen), bis(salicyla1dehyde)ethylene
M metal diimine
MCPA m-chloroperbenzoic acid t tertiary
Me methyl TBAF tetra(mbuty1)ammonium
Mes mesyl (methanesulphonyl) fluoride
min minutes TCNE tetracyanoethylene
MOM methox ymethyl TfO triflate
n normal THF tetrahydrofuran
Naph naphthyl Thi thien yl
NBA N-bromoacetamide THP tetrahydropyranyl
NBS N-bromosuccinimide TMEDA tetramethylethylene diamine
NHPI N-hydroxyphthalimide TMS trimethylsilyl
NMR nuclear magnetic resonance TMSCN trimethylsilyl cyanide
N.R. no reaction To1 tolyl
PDC pyridinium dichromate Tos tosyl( p-toluenesulphonyl)
Pent pentyl TPP triphenylphosphine
PI-N phthalimido Triton B benzyltrimethylammonium
Pip pideridyl hydroxide
Ph phenyl Trityl triphenylmeth yl
uv
PMR proton magnetic resonance irradiation with ultraviolet
PPA polyphosphoric acid light
Pr ProPYl XYI XYIYl
PY r pyridyl
