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Enantioselective Cobalt-catalysed Transformations

Enantioselective Cobalt-catalysed Transformations

Hélène Pellissier

(2018)

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Book Details

Abstract

With a foreword from leading organic chemist Professor Paul Wender, this book collects the major developments reported in the past thirty years in the field of enantioselective reactions promoted by chiral cobalt catalysts, illustrating the power of these green catalysts to provide all types of organic reactions from the basic to completely novel methodologies.

The search for new methodologies to prepare optically pure products is one of the most active areas of research in organic synthesis. Of the methods available for preparing chiral compounds, catalytic asymmetric synthesis has attracted the most attention. In particular, asymmetric transition-metal catalysis is a powerful tool for performing reactions in a highly enantioselective fashion. Efforts to develop new asymmetric transformations have previously focused on the use of rare metals such as titanium, palladium, iridium and gold. However, the ever-growing need for environmentally friendly catalytic processes has prompted chemists to focus on the more abundant and less toxic first-row transition metals, such as cobalt, to develop new catalytic systems.

The ability of cobalt catalysts to adopt unexpected reaction pathways has led to an impressive number of enantioselective cobalt-promoted transformations being developed over the past three decades. These have included the synthesis of many different types of products, often under relatively mild conditions and with remarkable enantioselectivities. This book is a useful reference resource for chemists, both academic and industrial, working in organic synthesis and interested in greener or more economical catalytic alternatives.


Table of Contents

Section Title Page Action Price
Cover Cover
Enantioselective Cobalt-catalysed Transformations i
Foreword vii
Abbreviations ix
Contents xiii
Chapter 1 - Enantioselective Cobalt-catalysed [2+1] Cycloadditions 1
1.1 Introduction 1
1.2 Cyclopropanations 1
1.2.1 Intermolecular Cyclopropanations 1
1.2.1.1 With Salen Cobalt Complexes 1
1.2.1.2 With Porphyrin Cobalt Complexes 10
1.2.1.3 With Other Cobalt Complexes 19
1.2.2 Intramolecular Cyclopropanations 20
1.3 Aziridinations and Epoxidations 22
1.3.1 Aziridinations 22
1.3.2 Epoxidations 26
1.4 Conclusions 28
References 29
Chapter 2 - Other Enantioselective Cobalt-catalysed Cycloadditions 34
2.1 Enantioselective Cobalt-Catalysed (Hetero)-Diels–Alder Cycloadditions 34
2.1.1 Diels–Alder Cycloadditions 34
2.1.2 Hetero-Diels–Alder Cycloadditions 36
2.2 Enantioselective Cobalt-Catalysed 1,3-Dipolar Cycloadditions 40
2.3 Enantioselective Cobalt-catalysed [2+2+2] and [2+2+1] Cycloadditions 46
2.3.1 [2+2+2] Cycloadditions 46
2.3.2 [2+2+1] Cycloadditions 50
2.4 Other Enantioselective Cobalt-Catalysed Cycloadditions 53
2.5 Conclusions 55
References 57
Chapter 3 - Enantioselective Cobalt-catalysed Cyclisations Through Domino Reactions 62
Conclusions 70
References 72
Chapter 4 - Miscellaneous Enantioselective Cobalt-catalysed Cyclisations 75
4.1 Using Salen Ligands 75
4.2 Using Biphosphine Ligands 84
4.3 Using Porphyrin Ligands 86
4.4 Using Other Ligands 88
4.5 Conclusions 92
References 93
Chapter 5 - Synthesis of Chiral Acyclic Compounds Through Enantioselective Cobalt-catalysed Reduction Reactions 95
5.1 Reductions of Carbonyl Compounds and Derivatives 95
5.1.1 Borohydride Reductions 95
5.1.2 Hydrosilylations 105
5.1.3 Hydrogenations 109
5.2 Reductions of Alkenes 111
5.2.1 Reductions with Borane Derivatives 111
5.2.1.1 Borohydride Conjugate Reductions 111
5.2.1.2 Hydroborations 115
5.2.2 Hydrosilylations 119
5.2.3 Hydrogenations 120
5.3 Conclusions 124
References 126
Chapter 6 - Synthesis of Chiral Acyclic Compounds Through Enantioselective Cobalt-catalysed Ring–Opening Reactions 129
6.1 Hydrolytic and Alcoholytic Ring–Opening of Epoxides 129
6.2 Ring–Opening of Epoxides by Amines and Carbamates 140
6.3 Ring–Opening of Epoxides Through (Co)polymerisation 143
6.4 Conclusions 146
References 147
Chapter 7 - Synthesis of Chiral Acyclic Compounds Through Enantioselective Cobalt-catalysed Michael and (Nitro)-Aldol Reactions 155
7.1 Michael Reactions 155
7.1.1 Michael Additions to α,β-Unsaturated Carbonyl Compounds and Derivatives 155
7.1.2 Michael Additions to Nitroolefins 160
7.2 (Nitro)-Aldol Reactions 167
7.3 Conclusions 175
References 175
Chapter 8 - Synthesis of Chiral Acyclic Compounds Through Enantioselective Cobalt-catalysed 1,2-Nucleophilic Additions to Carbonyl Compounds and Derivatives 178
Conclusions 185
References 186
Chapter 9 - Synthesis of Chiral Acyclic Compounds Through Enantioselective Cobalt-catalysed Cross-coupling Reactions 188
Conclusions 194
References 195
Chapter 10 - Synthesis of Chiral Acyclic Compounds Through Enantioselective Cobalt-catalysed Hydrovinylation Reactions 196
Conclusions 200
References 203
Chapter 11 - Synthesis of Chiral Acyclic Compounds Through Miscellaneous Enantioselective Cobalt-catalysed Reactions 204
11.1 α-Functionalisations and α-Alkylations of Carbonyl Compounds 204
11.2 Carbonyl-ene Reactions 207
11.3 Other Reactions 209
11.4 Conclusions 215
References 216
General Conclusion 218
Subject Index 220