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STEREOCHEMISTRY
EDITORS
ERNEST L. ELIEL
Professor of Chemistry
University of North Carolina
Chapel Hill, North Carolina
SAMUEL H. WILEN
Professor of Chemistry
Ciry College, City University of New York
New York, New York
VOLUME 18
AN INTERSCIENCE @ PUBLICATION
JOHN WILEY & SONS
New York 0 Chichester 0 Brisbane Toronto Singapore
TOPICS IN
STEREOCHEMISTRY
VOLUME I8
ADVISORY BOARD
STEREOCHEMISTRY
EDITORS
ERNEST L. ELIEL
Professor of Chemistry
University of North Carolina
Chapel Hill, North Carolina
SAMUEL H. WILEN
Professor of Chemistry
Ciry College, City University of New York
New York, New York
VOLUME 18
AN INTERSCIENCE @ PUBLICATION
JOHN WILEY & SONS
New York 0 Chichester 0 Brisbane Toronto Singapore
An InterscienceQ Publication
Copyright @ 1988 by John Wiley and Sons, Inc.
All rights reserved. Published simultaneously in Canada.
Reproduction or translation of any part of this work
beyond that permitted by Section 107 or 108 of the
1976 United States Copyright Act without the permission
of the copyright owner is unlawful. Requests for
permission or further information should be addressed to
the Permissions Department, John Wiley & Sons, Inc.
Library of Congress Catalog Card Number: 67-13943
ISBN 0-471-60026-1
Printed in the United States of America
10 9 8 7 6 5 4 3 2 1
To the 1987 Nobel Laureates in Chemistry
Donald J . Cram, Jean-Marie Lehn
and
Charles J . Pedersen
INTRODUCTION TO THE SERIES
In the first chapter in this volume William A. Bonner surveys the fascinating
research of scientists in several disciplines who have proposed hypotheses
and carried out experiments aimed at understanding the origins of the chiral
homogeneity of naturally occurring compounds. The stereochemical bias
giving rise to so many enantiomerically pure compounds in nature is but one
facet of the general question of the origin of life on earth. The range of
experiments and techniques applied to the solution of this problem is very
impressive. While there is not yet a definitive answer to the source of the
enantiomeric bias, we believe that readers will be pleased to have the key facts
and their interpretation as of 1987 presented and carefully reviewed by one of
the principal participants in this multidisciplinary research effort.
The second chapter, by N. A. Porter and P. J. Krebs, deals with radical pair
reactions. Both old and new stereochemical aspects of radical coupling are
examined from the perspective of kinetics as well a6 that of coupling equili-
bria. In a short but far ranging analysis the authors describe the fate of radical
pairs in solids and in other molecular aggregates (such as micelles) as well as
in solution.
In the third chapter Henri Brunner examines enantioselective syntheses of
organic compounds catalyzed by chiral transition metal compounds. In this
survey Brunner has focused on quantitative results reported during the three-
year period 1984-1986, during which a very large number of such syntheses
have been reported. Much of the data presented is in the form of tables which
are organized according to optically active catalyst ligands and reaction
product structures. We believe that this collection of data will be of help to
synthetic chemists, in particular, in the design of new stereoselective reac-
tions.
The fourth and last chapter in this volume is a review of kinetic resolution
by H. B. Kagan and J. C. Fiaud. This approach to optical activation, once
considered limited to enzymatic reactions, has in recent years become a very
practical way of preparing chiral compounds in nonracemic-even enan-
tiomericalljl pure-form by purely chemical processes. This turn of events is
in part due to recent developments leading to the very efficient kinetic
resolution of compounds that can serve as starting materials and as inter-
mediates in stereoselective syntheses of current interest. The seminal dis-
covery by Barry Sharpless et al. ( J . Amer. Chem. Soc., 1981, 203, 6237) of
asymmetric synthesis of optically active epoxides from allylic alcohols
ix
X PREFACE
xi
TOPICS IN
STEREOCHEMISTRY
VOLUME 18