Modern Organocopper Chemistry
.pdfModern 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
Copyright > 2002 Wiley-VCH Verlag GmbH
ISBNs: 3-527-29773-1 (Hardcover); 3-527-60008-6 (Electronic)
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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 Norbert Krause
Modern Organocopper Chemistry
Modern Organocopper Chemistry. Edited by Norbert Krause
Copyright > 2002 Wiley-VCH Verlag GmbH
ISBNs: 3-527-29773-1 (Hardcover); 3-527-60008-6 (Electronic)
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ISBN 3-527-29773-1 |
Modern Organocopper Chemistry. Edited by Norbert Krause
Copyright > 2002 Wiley-VCH Verlag GmbH
ISBNs: 3-527-29773-1 (Hardcover); 3-527-60008-6 (Electronic)
v
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
Copyright > 2002 Wiley-VCH Verlag GmbH
ISBNs: 3-527-29773-1 (Hardcover); 3-527-60008-6 (Electronic)
vii
Contents
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Foreword |
v |
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Preface |
xi |
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List of Authors xiii |
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1 |
Structures and Reactivities of Organocopper Compounds 1 |
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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 |
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1.4.2 |
Anionic Homoleptic and Heteroleptic Organocuprates |
32 |
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1.4.3 |
Lowerand Higher-order Cyanocuprates 34 |
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1.5 |
Concluding Remarks |
37 |
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Acknowledgement |
40 |
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References 40 |
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2 |
Transmetalation Reactions Producing Organocopper Reagents 45 |
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Paul Knochel, Bodo Betzemeier |
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2.1Introduction 45
2.2Transmetalation of Functionalized Organolithium and Organomagnesium Reagents 45
2.3 |
Transmetalation of Organoboron and Organoaluminium Reagents 51 |
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2.4 |
Transmetalation of Functionalized Organozinc Reagents 54 |
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2.4.1 |
Preparation of Organozinc Reagents |
54 |
2.4.1.1 |
Preparation of Organozinc Halides 56 |
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2.4.1.2 |
Preparation of Diorganozinc Reagents |
59 |
2.4.2 |
Substitution Reactions with Copper-Zinc Reagents 62 |
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2.4.3 |
Addition Reactions with Copper-Zinc Reagents 65 |
2.5Transmetalation of Organotin, Organosulfur, and Organotellurium Reagents 67
viii |
Contents |
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70 |
2.6 |
Transmetalation of Organotitanium and Organomanganese Reagents |
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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-
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Heteroatomalkylcuprates |
123 |
3.4.1 |
Simple Residual Ligands |
124 |
3.4.2 |
Chiral Ligands 127 |
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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 |
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4.2.1 |
Acceptor-substituted Dienes |
146 |
4.2.2 |
Acceptor-substituted Enynes |
150 |
4.2.3 |
Acceptor-substituted Polyenynes 159 |
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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 |
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Bruce H. Lipshutz |
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5.1 |
Introduction and Background |
167 |
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5.2 |
More Recent Developments: Stoichiometric Copper Hydride Reagents 168 |
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5.3 |
1,4-Reductions Catalytic in Cu(I) |
174 |
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5.4 |
1,2-Reductions Catalyzed by Copper Hydride |
179 |
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5.5 |
Heterogeneous CuH-Catalyzed Reductions |
182 |
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5.6 |
Overview and Future Developments 184 |
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References 185 |
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Contents ix
6Copper-mediated Diastereoselective Conjugate Addition and Allylic Substitution Reactions 188
Bernhard Breit, Peter Demel Abstract 188
6.1 |
Conjugate Addition 188 |
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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 |
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6.1.2.2 |
g-Alkyl-substituted a,b-Unsaturated Carbonyl Derivatives 198 |
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6.1.2.3 |
a,b-Unsaturated Carbonyl Derivatives with Stereogenic Centers in |
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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
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Complexes |
202 |
6.2 |
Allylic Substitution 210 |
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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 |
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7.3 |
Copper-catalyzed 1,4-Addition 229 |
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7.3.1 |
Phosphoramidite-based Catalysts 229 |
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7.3.2 |
Catalytic Cycle |
233 |
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7.3.3 |
Variation of Ligands |
234 |
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7.3.4 |
Cyclic Enones |
239 |
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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
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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 |
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8.3 |
Epoxides and Related Substrates 283 |
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8.4 |
Concluding Remarks |
286 |
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References and Notes |
286 |
9 |
Copper-Mediated Synthesis of Natural and Unnatural Products 289 |
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Yukiyasu Chounan, Yoshinori Yamamoto |
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Abstract 289 |
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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 |
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Seiji Mori, Eiichi Nakamura |
10.1Introduction 315
10.2 |
Conjugate Addition Reaction |
318 |
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10.2.1 |
Four-centered and Six-centered Mechanisms 318 |
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10.2.2 |
Single-electron Transfer Theorem |
319 |
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10.2.3 |
Kinetic and Spectroscopic Analysis of Intermediates |
320 |
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10.2.4 |
Catalytic Conjugate Addition |
322 |
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10.2.5 |
Theoretically Based Conjugate Addition Reaction Pathway |
322 |
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10.3 |
Carbocupration Reactions of Acetylenes and Olefins |
324 |
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10.3.1 |
Experimental Facts |
324 |
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10.3.2 |
Theoretically Based Carbocupration Reaction Pathway 325 |
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10.4 |
Substitution Reactions on Carbon Atoms |
327 |
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10.4.1 |
SN2 Mechanism of Stoichiometric Substitution Reactions |
327 |
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10.4.2 |
SN20 Allylation Reactions |
329 |
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10.4.3 |
Radical Substitution Reaction Mechanisms |
330 |
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10.4.4 |
Catalytic Substitution Reactions |
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330 |
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10.4.5 |
Theoretically Based Alkylation Reaction Pathways |
330 |
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10.6 |
Other Issues |
332 |
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10.6.1 |
Counter-cation Lewis Acid E ects |
332 |
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10.6.2 |
Me3SiCl Acceleration |
333 |
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10.6.3 |
Dummy Ligands |
335 |
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10.6.4 |
The ‘‘Higher Order’’ Cuprate Controversy |
337 |
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10.6.5 |
Further Issues |
338 |
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10.7 |
Orbital Interactions in Copper-mediated Reactions |
338 |
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10.8 |
The Roles of Cluster Structure in Copper-mediated Reactions 339 |
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10.9 |
Summary and Outlook |
340 |
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References |
340 |
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Author Index |
347 |
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Subject Index |
369 |
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