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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 |