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Catalysis in Asymmetric Synthesis

De
408 pages
Controlling the stereochemical outcome of reactions in the synthesis of complex natural products or bioactive materials represents a considerable intellectual and practical challenge for chemists. The stereochemical features of these products are usually essential to their bioactivity, so asymmetric synthesis has become a dominant feature of modern organic chemistry. Asymmetric catalysis is an important aspect of asymmetric synthesis, and one that has seen significant progress in the development of widely applicable methodology. This book is written from the point of view of the synthetic organic chemist, illustrating the transformations that can be achieved via this methodology, rather than the organometallic chemistry that lies behind. The emphasis is on non-enzymatic methods of asymmetric catalysis, although key references to enzyme-catalysed reactions have been incorporated where appropriate.

The book is extensively referenced and therefore provides a convenient point of entry to the primary literature for both experienced synthetic organic chemists and advanced students alike.

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Contents
Preface to the Second Edition Preface to the First Edition
1
2
3
Introduction 1.1 Reactions Amenable to Asymmetric Catalysis 1.2 Assignment of (R) and (S) Stereochemical Descriptors Futher Reading References
Reduction of Alkenes 2.1 Asymmetric Hydrogenation with Rhodium Complexes 2.2 Asymmetric Hydrogenation with Ruthenium Catalysts 2.3 Alkene Hydrogenation with Titanium and Zirconium Catalysts 2.4 Alkene Hydrogenation with Iridium Catalysts 2.5 Alkene Hydrogenation with Organocatalysts 2.6 Alkene Hydrosilylation 2.7 Alkene Hydroboration 2.8 Hydroamination 2.9 Hydroformylation 2.10 Hydroacylation of Alkenes 2.11 Hydrocyanation of Alkenes References
Reduction of Ketones and Imines 3.1 Hydrogenation of Ketones 3.2 Hydrogenation and Transfer Hydrogenation of Imines and Related Compounds 3.3 Transfer Hydrogenation of Ketones 3.4 Heterogeneous Hydrogenation 3.5 Reduction of Ketones Using Enantioselective Borohydride Reagents 3.6 Hydrosilylation of Ketones 3.7 Hydrosilylation of Imines and Nitrones References
xi xiii
1 1 2 6 7
9 9 18
24 25 28 29 32 34 36 39 40 40
47 47
53 56 59
63 68 73 75
vii
viii
4
5
6
7
8
Contents
Epoxidation 4.1 Epoxidation of Allylic Alcohols 4.2 Epoxidation with Metal(salen) Complexes 4.3 Epoxidation Using Metal–PorphyrinBased Catalysts 4.4 Other MetalCatalysed Epoxidations of Unfunctionalised Olefins 4.5 Epoxidation of ElectronDeficient Alkenes 4.6 Epoxidation with Iminium Salts 4.7 Epoxidation with Ketone Catalysts 4.8 Epoxidation of Aldehydes 4.9 Aziridination of Alkenes 4.10 Aziridination of Imines References
Further Oxidation Reactions 5.1 Dihydroxylation 5.2 Aminohydroxylation 5.3αHeterofunctionalisation of Aldehydes and Ketones 5.4 Oxidation of C–H 5.5 Baeyer–Villiger Oxidation 5.6 Oxidation of Sulfides References
Nucleophilic Addition to Carbonyl Compounds 6.1 Addition of Organozincs to Carbonyl Compounds 6.2 Addition of Cyanide to Aldehydes and Ketones 6.3 Allylation of Aldehydes 6.4 Hydrophosphonylation of Aldehydes 6.5 Nucleophilic Additions to Imines References
The Aldol and Related Reactions 7.1 The Aldol Reaction 7.2 Isocyanide and Related Aldol Reactions 7.3 The Nitroaldol Reaction 7.4 Addition of Enolates to Imines 7.5 Darzens Condensation 7.6 Morita–Baylis–Hillman Reaction 7.7 CarbonylEne Reactions References
Cycloadditions 8.1 Diels–Alder Reactions 8.2 Inverse Electron Demand Diels–Alder Reactions
81 81 88 94
95 96 101 102 105 106 108 109
117 117 126 130 136 138 139 142
147 147 153 160 165 166 173
179 180 191 193 195 200 201 203 208
213 213 231
9
10
11
12
Contents
8.3 HeteroDiels–Alder Reactions 8.4 1,3Dipolar Cycloaddition Reactions 8.5 [2+2] Cycloadditions 8.6 Pauson–KhandType Reactions References
Catalytic Reactions Involving Carbenes and Ylides 9.1 Cyclopropanation 9.2 Insertion Reactions 9.3 Asymmetric Ylide Reactions References
Catalytic Carbon–Carbon BondForming Reactions 10.1 CrossCoupling Reactions 10.2 MetalCatalysed Allylic Substitution 10.3 Heck Reactions 10.4 Alkylmetalation of Alkenes References
Conjugate Addition Reactions 11.1 Conjugate Addition of Enolates 11.2 Conjugate Addition of Sulfur Nucleophiles 11.3 Conjugate Addition of Nonstabilised Nucleophiles 11.4 Conjugate Addition with NitrogenBased Nucleophiles and Electrophiles References
Further Catalytic Reactions 12.1 Isomerisations and Rearrangements 12.2 Deprotonation Reactions 12.3 Protonation Reactions 12.4 Alkylation and Allylation of Enolates 12.5 Formation of Alkenes 12.6 OxyselenylationElimination Reactions 12.7 The Benzoin Condensation 12.8 Ester Formation and Hydrolysis 12.9 RingOpening of Epoxides References
Index
ix
232 240 246 249 251
257 257 268 273 275
281 282 284 296 302 305
311 311 317 320
325 328
333 333 336 336 338 342 344 344 345 349 355
361