Topics in Stereochemistry, Volume 21

540 Pages·1994·10.675 MB·English

TOPICS IN
STEREOCHEMISTRY
VOLUME 21
ADVISORY BOARD
STEPHEN J. ANGYAL, University ojNew South Wales,S ydney,A ustralia
ALAN R. BATTERSBY, Cambridge University, Cambridge, England
GIANCARLO BERTI, University of Pisa, Pisa, Italy
F. ALBERT COTTON, Texas A & M University, College Station, Texas
JOHANNES DALE, University of Oslo, Oslo, Norway
DAVID A. EVANS, Haruard University, Cambridge, Massachusetts
MEIR LAHAV, The Weizmann Institute of Science, Rehovoth, Israel
JEAN-MARIE LEHN, Collkge de France, Paris, France
MARIAN MIKOZAJCZYK, Centre of Molecular and Macromolecular
Studies, Polish Academy of Sciences, Xddi, Poland
KURT MISLOW, Princeton University, Princeton, New Jersey
MICHINORI OKI, Okayama University of Science, Okayama, Japan
VLADIMIR PRELOG, Eidgenossische Technische Hochschule, Zurich,
Switzerland
JOHN B. STOTHERS, University of Western Ontario, London, Ontario,
Canada
HANS WYNBERG, University of Groningen, Groningen, The Netherlands
NIKOLAI S. ZEFIROV, Moscow State University, Moscow, Russia
TOPICS IN
STEREOCHEMISTRY
EDITORS
ERNEST L. ELIEL
Professor of Chemistry, Emeritus
University of North Carolina
Chapel ffill, North Carolina
SAMUEL H. WILEN
Professor of Chemistry
City College, City University of New York
New York, New York
VOLUME 21
AN INTERSCIENCE@P UBLICATION
John Wiley & Sons, Inc.
NEW YORK ,/ CHICHESTER / BRISBANE / TORONTO / SINGAPORE
This text is printed on acid-free paper.
An Interscience" Publication
Copyright 0 1994 by John Wiley & 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., 605 Third Avenue, New York, NY
101 58-0012.
Library of Congress Catalog Card Number: 67-13943
ISBN 0-471-52120-5
Printed in the United States of America
10 9 8 7 6 5 4 3 2 I
To the memory of
Gunther Snatzke
INTRODUCTION TO THE SERIES
It is patently impossible for any individual to read enough of the journal
literature so as to be aware of all significant developments that may impinge
on his or her work, particularly in an area such as stereochemistry, which
knows no topical boundaries. Stereochemical investigations may have
relevance to an understanding of a wide range of phenomena and findings
irrespective of their provenance. Because stereochemistry is important in
many areas of chemistry, comprehensive reviews of high quality play a special
role in educating and alerting the chemical community to new stereochemical
developments.
The above considerations were reason enough for initiating a series such
as this. In addition of updating information found in such standard mono-
graphs as Stereochemistry of Carbon Compounds (Eliel, McGraw-Hill, 1962)
and Conformational Analysis (Eliel, Allinger, Angyal, and Morrison, Inter-
science, 1965; reprinted by American Chemical Society, 1981) as well as others
published more recently, the series is intended also to deal in greater detail
with some of the topics summarized in such texts. It is for this reason that
we have selected the title Topics in Stereochemistry for this series.
The series is intended for the advanced student, the teacher, and the active
researcher. A background of the basic knowledge in the field of stereo-
chemistry is assumed. Each chapter is written by an expert in the field and,
hopefully, covers its subject in depth. We have tried to choose topics of funda-
mental importance aimed primarily at an audience of inorganic and organic
chemists. Yet, many of these topics are concerned with basic principles of
physical chemistry and some deal with stereochemical aspects of biochemistry
as well.
We are fortunate in having been able to secure the help of an international
board of editorial advisors who have been of great assistance by suggesting
topics and authors for several chapters and by helping us avoid, insofar as
possible, duplication of topics appearing in other, related monograph series.
We are grateful to the editorial advisors for this assistance, but the editors
and authors alone must assume the responsibility for any shortcomings of
Topics in Stereochemistry.
E. L. ELIEL
S. H. WILEN
vii
PREFACE
The first of the five chapters in this volume, by E. Vedejs and E. J. Peterson,
is concerned with the stereochemistry and mechanism of the Wittig reaction.
An earlier chapter on the Wittig reaction, by M. Schlosser, appeared in
Volume 5 of this series, 23 years ago. Since then, not only has this extremely
useful reaction been most widely applied, but, especially in the last eight
years, there has been extensive work on its mechanism, notably by
M. Schlosser, by B. Maryanoff and by E. Vedejs himself. This work is not
only of great interest in its own right, but also, in as much as it leads to an
understanding of the stereochemical course of the Wittig reaction with a
wide variety of carbonyl compounds and ylides, it is of substantial importance
in organic synthesis. In fact, there are, in this chapter, extensive tabulations
of Wittig reactions that will no doubt prove valuable. Even so, and despite
a radical change of view concerning betaine intermediates in the Wittig
reaction, the last word concerning its general mechanism has apparently not
yet been spoken.
The second chapter, on the anomeric effect, by P, P. Graczyk and
M. Mikorajczyk, deals with another topic which, though by no means recent
in development, has been much in the news in the last few years and has even
been reviewed at regular intervals. Nonetheless, we believe that this scholarly
and extensive discussion of the effect in its conceptual, theoretical and applied
aspects will make an important contribution to the topic and lead to its
deeper understanding.
The third chapter, by Helena Dodziuk, deals with unusual saturated
hydrocarbons. This chapter is, in the main, an overview of theoretical
approaches to a series of “unnatural products”-most of them molecules,
real and hypothetical, with considerable strain-with a discussion of
important principles and an extensive list of references.
The fourth chapter, by Douglas W. Young, deals with an entirely different
topic, namely the steric course of metabolic reactions of a-amino acids.
Exploration of the stereochemistry of such reactions generally centers on
two questions: Which of two enantiotopic ligands (often enantiotopic
hydrogen atoms) is replaced or affected in a biological reaction and how
does the configuration of the product relate to the spatial disposition (topicity)
of the ligand displaced or affected? Again an earlier chapter by Arigoni and
Eliel in Volume 4 of this series (1969) dealt with this topic in a general way
ix
X PREFACE
and once more the literature has mushroomed to the point where this timely
chapter deals with an extensive and important subset of the examples of
24 years ago.
The last chapter, by M. G. Bures, C. Martin and P. Willett, in contrast,
Y.
deals with a very recent and novel subject, namely the searching of databases
of chemical structures in three dimensions. It is only in the last few years
that extensive three-dimensional databases (other than records of molecular
structures determined by X-ray crystallography or other techniques) have
been constructed. The question, to which much ingenuity has been applied,
is how to search such databases for structures with a specific spatial
relationship of ligands, for example one believed to be conducive to a desired
pharmacological activity. The answer is not easy to come by, especially in
view of the fact that many potential candidate molecules display several
low-lying energy minima corresponding to different conformations, and the
conformation expected to be active may not be the one corresponding to
the global energy minimum. This chapter gives an authoritative picture of
the present state of the art in this field.
It is with great sorrow that we must report the death, on January 14,
1992, of our advisor Gunther Snatzke. Professor Snatzke was not only a
personal friend of both of the editors, he was also an unusually active and
effective advisor. Several chapters in recent volumes were commissioned at
his suggestion; and he himself had planned to contribute a chapter on aspects
of circular dichroism to Volume 21. But this was not to be. We dedicate this
volume to the memory of Gunther Snatzke whom we shall miss.
In conclusion, a more upbeat note: The manuscript of our long expected
“Stereochemistry of Organic Compounds” book finally went to the publisher
(Wiley) late last year and we expect that the book will appear at about the
same time as this volume.
ERNESTL . ELIEL
Chapel Hill, North Carolina SAMUELH . WILEN
New York, New York
Novemher 1993
CONTENTS
STEREOCHEMISTRY AND MECHANISM OF THE WITTIG
REACTION 1
by E. Vedejs and M. J. Peterson
Department of Chemistry
University of Wisconsin
Madison, Wisconsin
ANOMERIC EFFECT: ORIGIN AND CONSEQUENCES 15 9
by Piotr R. Graczyk and Marian Mikdajczyk
Department of Organic Sulfur Compounds
Center of Molecular and Macromolecular Studies
Polish Academy of Science
Xodi. Poland
UNUSUAL SATURATED HYDROCARBON!$ INTERACTION
BETWEEN THEORETICAL AND SYNTHETIC
CHEMISTRY 35 1
by Helena Dodziuk
Institute of Organic Chemistry
Polish Academy of Sciences
Warsaw, Poland
STEREOCHEMISTRY OF METABOLIC REACTIONS OF
AMINO ACIDS 381
by Douglas W. Young
School of Chemistry and Molecutar Sciences
University of Sussex
Falmer, Brighton, United Kingdom
SEARCHING TECHNIQUES FOR DATABASES OF THREE-
DIMENSIONAL CHEMICAL STRUCTURES 467
by Mark G. Bures and Yvonne C. Martin
Computer-A ssisted Molecular Design Project
Abbott Laboratories
Abbott Park. Illinois;
xi
xii CONTENTS
and Peter Wiflett
Krebs Institute for Biomolecular Research and Department
of Information Studies
University of Shefield
Shefleld. United Kingdom
CUMULATIVE TITLE INDEX, VOLUMES 1-21 513
SUBJECT INDEX 519