General and Synthetic Methods Volume 16

620 Pages·1994·8.854 MB·English

General and Synthetic Methods
Volume 16

A Specialist Periodical Report
General and Synthetic
Methods
Volume 16
A Review of the Literature Published between January
1991 and July 1992
Senior Reporter
G. Pattenden, Department of Chemistry, University of Nottingham
Reporters
R.P.C. Cousins, Glaxo Group Research, Greenf ord, Middx.
L.P. Crawford, SmithKline Beecham, Welwyn, Herts.
T. Harrison, Merck Sharpe & Dohme, Harlow, Essex
D.C. Harrowven, University of Nottingham
M.J. Kiefel, University of Nottingham
J.D. Kilburn, University of Southampton
C.F. Marcos, Imperial College of Science, Technology and Medicine,
London
S. Perrio, Imperial College, London
0. Riant, lmperial College, London
S.K. Richardson, Notre Dame University, Notre Dame, Indiana, USA
G.M. Robertson, Glaxo Group Research, Ware, Herts.
J. Steele, Pfizer Central Research, Sandwich, Kent
S.D.A. Street, Pfizer Central Research, Sandwich, Kent
J.B. Sweeney, University of Bristol
S.E. Thomas, Imperial College of Science, Technology and Medicine,
London
M. Wills, University of Bath
SOCIETY OF
CHEMISTRY
ISBN 0-85186-834-7
ISSN 0141-2140
0T he Royal Society of Chemistry 1994
All Rights Reserved
No part of this book may be reproduced or transmitted in any form
or by any means -graphic, electronic, including photocopying, recording,
taping, or information storage and retrieval systems - without written
permission from The Royal Society of Chemistry
Published by The Royal Society of Chemistry, Thomas Graham House,
Science Park, Milton Road, Cambridge CB4 4WF
Printed in Great Britain by
Athenaeum Press Ltd, Newcastle upon Tyne
In trod uction
This sixteenth Report will be the last Volume in the RSC's Specialist Periodical Report series of
General arid Syrithetic Methods. Volume 16 covers the literature published over the period January
1991-July 1992, except for the chapter on "Carboxylic Acids and Derivatives" which provides
coverage of the literature throughout 1990 and 1991 only.
Starting in January 1994, the new RSC review journal Contemporary Organic Synthesis will act as a
natural successor to Getieral arid Sytirhetic Methods, and the journal will cover all the regular literature
that has been included in the Specialist Periodical Report. There will be complete continuity of
coverage between the two publications over the first few years, but Coritenipoiuiy Oipmic Synthesis
also aims to provide a more extended coverage of the literature of synthesis on a more regular basis
and with minimum delays in publication.
Contemporary Organic Syrithesis will review and provide perspective on all aspects of methodology,
selectivity and efficiency in contemporary synthesis. As well as covering all the principles and
methods in functional group chemistry and interconversions,o rganomstallic chemistry and asymmetric
synthesis will feature prominently, as will modern aspects of strategy and computer-aided design,
biotransformations and protecting group protocols. Special methods and techniques, such as
sonochemistry, FVP, electroorganic synthesis, and supported catalysis will be included as occasional
articles, and the manner in which synthesis addresses problems and provides solutions in biology,
medicine, agriculture and new materials will also be encompassed.
The new Join-rid will contain a number of "key features". It will:
provide regular, up-to-date coverage of all major functional group interconversions - highlighting
the best methods and making meaningful comparisons.
address the problems of chemo-, regio- and stereoselectivity in modem synthesis.
discuss the design and development of chiral auxiliaries, catalytic asymmetric processes and
biological methods.
highlight the scope for organometallic reagents in rational, efficient design.
provide timely reviews of the place of synthesis in all areas of natural product chemistry,
medicine, apiculture and materials science.
encompass developments at the cutting edge of molecular recognition phenomena,
supramolecular chemistry and self-assembly processes.
address the needs of modern industry and the industrial chemist, taking into account economic
and environmental factors.
vi Introduction
Conteniyoi-my Organic Synthesis will lead the field, and will be the first review journal devoted
specifically to surveying this area. The new journal will be an essential reference source for all those
with an interest in organic compounds and their synthesis.
In closing this final volume of Gene/-a1a rid Syrithefic Methods, it only remains for me to thank the
numerous contributors to the series, together with the editorial staff at the RSC, for their unstinting
efforts and their enthusiastic collaboration over the past seventeen years. Thank you.
November 1993
G. Pattenden
Cont ents
Chapter 1 Saturated and Unsaturated Hydrocarbons 1
By R.P.C. Cousins
Saturated Hydrocarbons
Olefinic Hydrocarbons
Stereoselective, Simultaneous Formation
of sp3 and sp2 Centres 9
Claisen Rearrangements 9
[2,3] Wittig Rearrangements 11
Conjugated Dienes 11
Non-conjugated Dienes 17
Poly enes 17
Allenes 24
Alkynes 24
Enynes 27
References 32
Chapter 2 Aldehydes and Ketones 37
By L.P . Crawford and S.K . Richardson
1 Synthesis of Aldehydes and Ketones 37
Oxidative Methods 37
Reductive Methods 40
Methods Involving Umpolung 43
Other Methods 43
Cyclic Ketones 46
Vl.l.l. Gcneral and Synthetic Methods
2 Synthesis of Functionalised Aldehydes and Ketones 53
Unsaturated Aldehydes and Ketones 53
a-Substituted Aldehydes and Ketones 59
Dicarbonyl Compounds 64
3 Protection and Deprotection of Aldehydes and
Ketones 69
4 Reactions of Aldehydes and Ketones 71
Reactions of Enolates 71
Aldol Reactions 73
Conjugate Addition Reactions 78
References 84
Chapter 3 Carboxylic Acids and Derivatives 92
By T. Harrison
1 Carboxylic Acids 92
General Synthesis 92
Diacids 94
Hydrox y-acids 96
Keto-acids 98
Unsaturated Acids 98
Aromatic Acids 101
Halo-acids 101
Carboxylic Acid Protection 101
2 Carboxylic Acid Esters 102
Esteri fication 102
General Synthesis 103
Diesters 105
H ydrox y-esters 107
Keto-esters 110
Unsaturated Esters 115
Halo-esters 117
Thioesters 119
3 Carboxylic Acid Amides 119
General Synthesis 119
Hy drox y -amides 123
Keto-amides 123
Unsaturated Amides 123
Thioamides 125