Methodologies in Asymmetric Catalysis

214 Pages·2004·17.86 MB·English

by  Sanjay V. Malhotra (Eds.)

Methodologies in Asymmetric
Catalysis
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In Methodologies in Asymmetric Catalysis; Malhotra, S.;
ACS Symposium Series; American Chemical Society: Washington, DC, 2004.
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In Methodologies in Asymmetric Catalysis; Malhotra, S.;
ACS Symposium Series; American Chemical Society: Washington, DC, 2004.
ACS SYMPOSIUM SERIES 880
Methodologies in Asymmetric
Catalysis
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88 Sanjay V. Malhotra, Editor
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Sponsored by the
ACS Division of Organic Chemistry
American Chemical Society, Washington, DC
In Methodologies in Asymmetric Catalysis; Malhotra, S.;
ACS Symposium Series; American Chemical Society: Washington, DC, 2004.
QD 262 .M53 2004 copy 1
Methodologies in asymmetric
catalysis
Library of CongressC ataloging-in-Publication Data
Methodologies in asymmetric catalysis / Sanjay V. Malhotra, editor ; sponsored by the
ACS Division of Organic Chemistry.
p. cm.—(ACS symposium series ; 880)
Includes bibliographical references and index.
ISBN 0-8412-3835-9 (alk. paper)
1. Asymmetric synthesis—Congresses. 2. Catalysis—Congresses.
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0 I. Malhotra, Sanjay V. II. American Chemical Society. Division of Organic Chemistry. III
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w American Chemical Society. Meeting (223rd : 2002 : Orlando, Fla.) IV. Series.
0.f
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08 D262.M53 2004
04- 547'.2—dc22 2004046177
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2
bk- The paper used in this publication meets the minimum requirements of American
1/ National Standard for Information Sciences—Permanence of Paper for Printed Library
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10 Materials, ANSI Z39.48-1984.
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g doi: Copyright © 2004 American Chemical Society
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6, 2cati permission requests to ACS Copyright Office, Publications Division, 1155 16th St.,
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PRINTED IN THE UNITED STATES OF AMERICA
In Methodologies in Asymmetric Catalysis; Malhotra, S.;
ACS Symposium Series; American Chemical Society: Washington, DC, 2004.
Foreword
The ACS Symposium Series was first published in 1974 to pro­
vide a mechanism for publishing symposia quickly in book form. The
purpose of the series is to publish timely, comprehensive books devel­
oped from ACS sponsored symposia based on current scientific re­
search. Occasionally, books are developed from symposia sponsored by
other organizations when the topic is of keen interest to the chemistry
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0 audience.
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8 tents is reviewed for appropriate and comprehensive coverage and for
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04- interest to the audience. Some papers may be excluded to better focus
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k- the book; others may be added to provide comprehensiveness. When
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1 chapters are peer-reviewed prior to final acceptance or rejection, and
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In Methodologies in Asymmetric Catalysis; Malhotra, S.;
ACS Symposium Series; American Chemical Society: Washington, DC, 2004.
Preface
This book is based on papers presented at the American Chemical
Society (ACS) national meeting symposium titled New Methodologies in
Asymmetric Catalysis, held in Orlando, Florida, April 7-11, 2002.
Asymmetric catalysis has been one of the important topics of research for
scientist in both industrial laboratories and the academic world during the
past three decades. This symposium was the first open international
meeting on asymmetric catalysis, since the announcement of a Nobel
Prize in Chemistry for 2001, which was shared by three scientists
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0 (William S. Knowles, Ryoji Noyori, and K. Barry Sharpless) for their
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0.pr pioneering work in this field. The sessions at the ACS symposium on this
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08 topic were the best attended at the meeting, which is a clear indication of
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0 the interest in and importance of the subject. This monograph includes
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1/ who have made significant contribution in the field of asymmetric
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0.1 catalysis.
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oi: The symposium would not have been successful without
cs.org 004 | d pinrovfaelussaibolnea l sourpgpaonritz atiforonms. Tthhee syfmolplooswiuinmg waacs ahdoesmteidc , anidn dsupsotnrsiaolr,e d abnyd
bs.a4, 2 the ACS Division of Organic Chemistry. Additional financial support for
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6, 2cati Chemicals, Inc., Synthon Chiragenics Corporation, Strem Chemicals,
st 1ubli Callery Chemical, Engelhard Corporation, Sorbent Technologies, and
uP
ug Aldrich Chemical Company. I am indebted to the presenters at the
A
symposium, to the authors who contributed to this book, and to these
organizations for their foresight in sponsoring this symposium and I am
looking forward to continuing to work with them.
Sanjay V. Malhotra
Department of Chemistry and Environmental Science
New Jersey Institute of Technology
University Heights
Newark, NJ 07102-1982
ix
In Methodologies in Asymmetric Catalysis; Malhotra, S.;
ACS Symposium Series; American Chemical Society: Washington, DC, 2004.
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In Methodologies in Asymmetric Catalysis; Malhotra, S.;
ACS Symposium Series; American Chemical Society: Washington, DC, 2004.
Methodologies in Asymmetric
Catalysis
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In Methodologies in Asymmetric Catalysis; Malhotra, S.;
ACS Symposium Series; American Chemical Society: Washington, DC, 2004.
Chapter 1
Chiral Dirhodium(II) Carboxamidates
for Catalytic Asymmetric Synthesis
Michael P. Doyle
Department of Chemistry, University of Arizona, Tucson, AZ 85721
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10. also including Lewis acid catalyzed reactions. High
oi: selectivities are achieved even with low catalyst loadings, and
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The Catalysts
Dirhodium(II) carboxamidate catalysts are constructed from dirhodium(II)
acetate by ligand replacement (eql)(/-3). Since the amide ligands are more
4LH + Rh(OAc) *ff » RhL + 4HOAc (1)
2 4 v 2 4
reflux (trapped with
NaC0)
2 3
© 2004 American Chemical Society 1
In Methodologies in Asymmetric Catalysis; Malhotra, S.;
ACS Symposium Series; American Chemical Society: Washington, DC, 2004.
2
susceptible to replacement in an acidic medium, the removal of acetic acid is the
key element in the success of this replacement reaction. This is accomplished
by trapping acetic acid as it forms ^Soxhelet extractor containing sodium
carbonate).
Four classes of dirhodium(II) carboxamides have been synthesized, and
they are illustrated in Scheme 1: MEPY = methyl 2-oxopyrrolidine-carboxylate
(4), MEOX = methyl 2-oxooxazolidine-carboxylate (5), MPPIM = methyl 3-
phenylpropanoyl-2-oxoimidazolidine-carboxylate (d), and IBAZ = isobutyl 2-
oxoazetidine-carboxylate (7). These catalysts are constructed with four bridging
ligands so that two nitrogens and two oxygens reside on each rhodium, and the
nitrogens (or oxygens) are cis to each other. This places the carboxylate
attachment in two adjacent quadrants and allows convenient access to the
substrate bound to the axial site of rhodium.
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A
Scheme 1
Their preparation commonly results in the crystallization of the bis-
acetonitrile complex in which acetonitriles occupy the axial coordination sites.
These materials are then resistant to hydrolysis and to air oxidation, and they
have been stored intact for several years.
The reactivities of these catalysts are less then those of dirhodium(II)
carboxylates, but among the classes of carboxamidates in Scheme 1 there is
significant variation. Azetidinone-ligated dirhodium catalysts like Rh2(45-
IBAZ)4 are the most reactive in an electrophilic sense. This is because the
ligand NCO angle is larger, and its bite on dirhodium(II) lengthens the rhodium-
rhodium bond (7).
In Methodologies in Asymmetric Catalysis; Malhotra, S.;
ACS Symposium Series; American Chemical Society: Washington, DC, 2004.