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Modern Organocopper Chemistry. Edited by Norbert Krause Copyright > 2002 Wiley-VCH Verlag GmbH ISBNs: 3-527-29773-1 (Hardcover); 3-527-60008-6 (Electronic)

Edited by N. Krause

Modern Organocopper

Chemistry

Modern Organocopper Chemistry. Edited by Norbert Krause

ISBNs: 3-527-29773-1 (Hardcover); 3-527-60008-6 (Electronic)

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Modern Organocopper Chemistry. Edited by Norbert Krause

ISBNs: 3-527-29773-1 (Hardcover); 3-527-60008-6 (Electronic)

Edited by Norbert Krause

Modern Organocopper Chemistry

Modern Organocopper Chemistry. Edited by Norbert Krause

ISBNs: 3-527-29773-1 (Hardcover); 3-527-60008-6 (Electronic)

Editor	9	This book was carefully produced.
		Nevertheless, editor, authors and publisher
Prof. Dr. N. Krause		do not warrant the information contained
University of Dortmund		therein to be free of errors. Readers are
Organic Chemistry II		advised to keep in mind that statements,
D-44221 Dortmund		data, illustrations, procedural details or
Germany		other items may inadvertently be
		inaccurate.
		Library of Congress Card No.: applied for
		British Library Cataloguing-in-Publication
		Data
		A catalogue record for this book is available
		from the British Library.
		Die Deutsche Bibliothek – CIP Cataloguing-
		in-Publication Data
		A catalogue record for this publication is
		available from Die Deutsche Bibliothek
		( 2002 WILEY-VCH GmbH, Weinheim
		All rights reserved (including those of
		translation in other languages). No part of
		this book may be reproduced in any form –
		by photoprinting, microﬁlm, or any other
		means – nor transmitted or translated into
		a machine language without written
		permission from the publisher. Registered
		names, trademarks, etc. used in this book,
		even when not speciﬁcally marked as such,
		are not to be considered unprotected by
		law.
		Printed in the Federal Republic of
		Germany
		Printed on acid-free paper
		Composition Asco Typesetters, Hong
		Kong
		Printing Strauss O setdruck GmbH
		Mo¨rlenbach
		Bookbinding Wilhelm Osswald & Co.,
		Neustadt
		ISBN 3-527-29773-1

Modern Organocopper Chemistry. Edited by Norbert Krause

ISBNs: 3-527-29773-1 (Hardcover); 3-527-60008-6 (Electronic)

Foreword

Copper is one of the oldest transition metals to be used in synthetic organic chemistry. Starting in the 60’s, organocopper reagents became among the most popular synthetic tools in the total synthesis of natural product. This is due to the ease of handling and to the chemo-, regioand stereoselectivities attained with these reagents. Their unique properties for the conjugate addition, for the clean SN2 substitution, for the mild opening of epoxides, for the carbometallation of triple bonds, etc . . . makes them unavoidable reagents for these synthetic transformations.

Over the years, a whole family of reagents evolved with increased selectivity and reactivity. ‘‘Homocuprates’’, ‘‘heterocuprates’’, ‘‘higher order cuprates’’, ‘‘mixed cuprates’’, and others, are terms often employed, and a newcomer chemist may worry about their di erent properties. Despite a lot of progress in the area of organocopper chemistry there is still a strong lack of knowledge in the mechanistic insights. No reactive intermediates have been trapped, and this ‘‘black box’’ was only considered through analogies with other closely related transition metals or, more recently, through extensive calculations. This is to say that all our knowledge about organocopper chemistry did not came by rational design but through empirical way with experimentation.

Over the years, several review articles appeared on organocopper chemistry. Most often, they cover some aspects or some restricted class of reagents, and they are addressed to chemists knowing already the main reactions of organocopper reagents. In contrast to other transition metals, such as Pd, Ni, Rh etc . . . only few books, covering the entire area of organocopper chemistry, have been published. The present book is the most comprehensive and all the most recent advances are extensively discussed: Zn-Cu reagents, Sn and Si-Cu reagents, H-Cu reagents, asymmetric reactions. The reader will learn about the structure of organocopper reagents and about the most updated mechanistic beliefs presently known.

Organocopper chemistry is of wide applicability, very e cient and easy to perform. The main problem is to know the most appropriate reagent to use. The reader will ﬁnd in this book all the details for the reagent of choice, for the scope and limitations, for the type of substrate needed. This book should be helpful not only to advanced research chemists, but also for teaching this chemistry to younger

vi Foreword

students in a comprehensive and modern way. Such a wide coverage of an important piece of chemistry is not only welcome; it was needed!

December 2001

Professor Alexandre Alexakis

University of Geneva

Geneva

Modern Organocopper Chemistry. Edited by Norbert Krause

ISBNs: 3-527-29773-1 (Hardcover); 3-527-60008-6 (Electronic)

vii

Contents

	Foreword	v
	Preface	xi
	List of Authors xiii
1	Structures and Reactivities of Organocopper Compounds 1
	Johann T. B. H. Jastrzebski, Gerard van Koten

1.1Introduction 1

1.1.1	Historical Perspective 1
1.1.2	The Oxidation States of Copper 3
1.1.3	Thermal Stability and Bonding in Organocopper(I) Compounds 6
1.2	Homoleptic Organocopper Compounds CunRn 8
1.3	Heteroleptic Organocopper Compounds CunBmRnXm 17

1.4Organocuprates 26

1.4.1	Neutral Homoleptic and Heteroleptic Organocuprates		27
1.4.2	Anionic Homoleptic and Heteroleptic Organocuprates		32
1.4.3	Lowerand Higher-order Cyanocuprates 34
1.5	Concluding Remarks	37
	Acknowledgement	40
	References 40
2	Transmetalation Reactions Producing Organocopper Reagents 45
	Paul Knochel, Bodo Betzemeier

2.1Introduction 45

2.2Transmetalation of Functionalized Organolithium and Organomagnesium Reagents 45

2.3	Transmetalation of Organoboron and Organoaluminium Reagents 51
2.4	Transmetalation of Functionalized Organozinc Reagents 54
2.4.1	Preparation of Organozinc Reagents	54
2.4.1.1	Preparation of Organozinc Halides 56
2.4.1.2	Preparation of Diorganozinc Reagents	59
2.4.2	Substitution Reactions with Copper-Zinc Reagents 62
2.4.3	Addition Reactions with Copper-Zinc Reagents 65

2.5Transmetalation of Organotin, Organosulfur, and Organotellurium Reagents 67

viii	Contents
			70
2.6		Transmetalation of Organotitanium and Organomanganese Reagents	70
2.7		Transmetalation of Organozirconium and Organosamarium Reagents	71

2.8Conclusion 74

References 75

3	Heteroatomcuprates and a-Heteroatomalkylcuprates in Organic Synthesis 79

R. Karl Dieter

3.1Introduction 79

3.2Heteroatomcuprates 80

3.2.1	Group IVA Heteroatoms (Si, Ge, Sn) 80
3.2.1.1	Conjugate Addition Reactions 83
3.2.1.2	Silylcupration and Stannylcupration of Alkynes and Allenes 93
3.2.1.3	Substitution Reactions 102
3.2.2	Group VA and VIA Heteroatoms (N, O, P) 108

3.3a-Heteroatomalkylcuprates 109

3.3.1	Group VI Heteroatoms (O, S, Se) 110
3.3.2	Group V Heteroatoms (N, P) and Silicon 114
3.3.3	a-Fluoroalkylcuprates and a-Fluoroalkenylcuprates 122

3.4Non-transferable Heteroatom(alkyl)cuprates and a-

	Heteroatomalkylcuprates	123
3.4.1	Simple Residual Ligands	124
3.4.2	Chiral Ligands 127

3.5Summary 133 Acknowledgments 134 References 134

4Copper-mediated Addition and Substitution Reactions of Extended Multiple

Bond Systems 145

Norbert Krause, Anja Ho mann-Ro¨der

4.1Introduction 145

4.2	Copper-mediated Addition Reactions to Extended Michael Acceptors 146
4.2.1	Acceptor-substituted Dienes	146
4.2.2	Acceptor-substituted Enynes	150
4.2.3	Acceptor-substituted Polyenynes 159
4.3	Copper-mediated Substitution Reactions of Extended Substrates 160

4.4Conclusion 162

References 163

5	Copper(I)-mediated 1,2- and 1,4-Reductions 167
	Bruce H. Lipshutz
5.1	Introduction and Background	167
5.2	More Recent Developments: Stoichiometric Copper Hydride Reagents 168
5.3	1,4-Reductions Catalytic in Cu(I)	174
5.4	1,2-Reductions Catalyzed by Copper Hydride		179
5.5	Heterogeneous CuH-Catalyzed Reductions		182
5.6	Overview and Future Developments 184
	References 185

Contents ix

6Copper-mediated Diastereoselective Conjugate Addition and Allylic Substitution Reactions 188

Bernhard Breit, Peter Demel Abstract 188

6.1	Conjugate Addition 188
6.1.1	Stereocontrol in Cyclic Derivatives	188
6.1.2	Stereocontrol in Acyclic Derivatives	192
6.1.2.1	g-Heteroatom-substituted Michael Acceptors 192
6.1.2.2	g-Alkyl-substituted a,b-Unsaturated Carbonyl Derivatives 198
6.1.2.3	a,b-Unsaturated Carbonyl Derivatives with Stereogenic Centers in
	Positions other than the g-Position	200
6.1.2.4	Directed Conjugate Addition Reactions 200

6.1.3Auxiliary-bound Chiral Michael Acceptors and Auxiliary Chiral Metal

	Complexes	202
6.2	Allylic Substitution 210
	References	218

7Copper-catalyzed Enantioselective Conjugate Addition Reactions of Organozinc Reagents 224

Ben L. Feringa, Robert Naasz, Rosalinde Imbos, Leggy A. Arnold

7.1Introduction 224

7.2	Organozinc Reagents		227
7.3	Copper-catalyzed 1,4-Addition 229
7.3.1	Phosphoramidite-based Catalysts 229
7.3.2	Catalytic Cycle	233
7.3.3	Variation of Ligands		234
7.3.4	Cyclic Enones	239

7.3.52-Cyclopentenone 240

7.3.6	Acyclic Enones 242
7.4	Synthetic Applications 243
7.4.1	Tandem Conjugate Addition-Aldol Reactions 243
7.4.2	Kinetic Resolution of 2-Cyclohexenones 243
7.4.3	Sequential 1,4-Additions to 2,5-Cyclohexadienones 246

7.4.4Lactones 250

7.4.5Nitroalkenes 250

7.4.6 Annulation Methodology 252

7.5Conclusions 254 Acknowledgements 255

	References and Notes 255
8	Copper-Mediated Enantioselective Substitution Reactions 259

A. Soﬁa E. Karlstro¨m, Jan-Erling Ba¨ckvall

8.1Introduction 259

8.2	Allylic Substitution 261
8.2.1	Allylic Substrates with Chiral Leaving Groups 262
8.2.2	Chiral Auxiliary that is Cleaved o after the Reaction 268

xContents

8.2.3	Catalytic Reactions with Chiral Ligands 272
8.3	Epoxides and Related Substrates 283
8.4	Concluding Remarks	286
	References and Notes	286
9	Copper-Mediated Synthesis of Natural and Unnatural Products 289
	Yukiyasu Chounan, Yoshinori Yamamoto
	Abstract 289
9.1	Conjugate Addition	289
9.2	SN2 Substitution 296

9.3SN20 Substitution 302

9.4	1,2-Metalate Rearrangements 306

9.5Carbocupration 309 References 310

10	Mechanisms of Copper-mediated Addition and Substitution Reactions 315
	Seiji Mori, Eiichi Nakamura

10.1Introduction 315

10.2	Conjugate Addition Reaction					318
10.2.1	Four-centered and Six-centered Mechanisms 318
10.2.2	Single-electron Transfer Theorem						319
10.2.3	Kinetic and Spectroscopic Analysis of Intermediates								320
10.2.4	Catalytic Conjugate Addition					322
10.2.5	Theoretically Based Conjugate Addition Reaction Pathway									322
10.3	Carbocupration Reactions of Acetylenes and Oleﬁns								324
10.3.1	Experimental Facts			324
10.3.2	Theoretically Based Carbocupration Reaction Pathway 325
10.4	Substitution Reactions on Carbon Atoms							327
10.4.1	SN2 Mechanism of Stoichiometric Substitution Reactions									327
10.4.2	SN20 Allylation Reactions				329
10.4.3	Radical Substitution Reaction Mechanisms							330
10.4.4	Catalytic Substitution Reactions						330
10.4.5	Theoretically Based Alkylation Reaction Pathways								330
10.6	Other Issues	332
10.6.1	Counter-cation Lewis Acid E ects						332
10.6.2	Me3SiCl Acceleration			333
10.6.3	Dummy Ligands		335
10.6.4	The ‘‘Higher Order’’ Cuprate Controversy							337
10.6.5	Further Issues		338
10.7	Orbital Interactions in Copper-mediated Reactions								338
10.8	The Roles of Cluster Structure in Copper-mediated Reactions 339
10.9	Summary and Outlook				340
	References	340
	Author Index	347
	Subject Index	369

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