Synthetic and Stereochemical Aspects (eBook)

Cover 1
Contents 8
List of Contributors 12
Preface 14
Chapter 1. Asymmetric Sulfoxidation–Chemical and Enzymatic 16
1.1 Introduction 17
1.2 Oxidation of sulfides bearing a removable chiral auxiliary 18
1.3 Stoichiometric enantioselective oxidation of sulfides 23
1.4 Catalytic chemical asymmetric sulfoxidation 33
1.5 Biosulfoxidations 42
1.6 Kinetic resolution 45
1.7 Conclusion 49
References 49
Chapter 2. The Synthesis of Chiral Sulfoxides through Nucleophilic Displacement at Sulfur 56
2.1 Introduction 56
2.2 The Andersen procedure for the synthesis of enantiomerically enriched, chiral sulfoxides 56
2.3 Adaptations of the Andersen procedure 59
2.4 Application of chiral sulfinamides 63
2.5 Application of chiral, cyclic sulfinamides 67
2.6 Application of chiral, cyclic sulfites 73
References 75
Chapter 3. Conformational Preference of the Sulfinyl Group in Six-Membered Heterocycles 78
3.1 Introduction 79
3.2 Conformational equilibria of thiane-l-oxides 80
3.3 Conformational analysis of oxathiane S-oxides 91
3.4 Conformational analysis of dithiane S-oxides 95
3.5. Conformational analysis of 5-sulfinyl-1,3-dioxanes 101
3.6 Conformational analysis of 2-oxo-1,3,2-dioxathianes 105
References 106
Chapter 4. Applications of Chiral Sulfoxides as Stereocontrol Elements in Organic Synthesis 112
4.1 Stereoselective reduction of ß-ketosulfoxides: some applications in organic synthesis 114
4.2 Stereocontrolled reactions of iminosulfoxides 124
4.3 The stereocontrolled addition of nucleophiles to chiral vinylic sulfoxides 136
4.4 Miscellaneous reaction types amenable to stereocontrol by acyclic chiral sulfoxides 148
4.5 Cyclic sulfoxides in organic synthesis 149
4.6 Application of chiral sulfoxides to the synthesis of natural products 162
4.7 Concluding remarks 166
References 166
Chapter 5. The Chemistry of a,ß - unsaturated Sulfoxides 172
5.1 Introduction 173
5.2 Preparation of optically active a,ß -unsaturated sulfoxides 173
5.3 Electrophilic additions to a,ß -unsaturated sulfoxides 179
5.4 Nucleophilic additions to a,ß-unsaturated sulfoxides 186
5.5 Pericyclic reactions of a,ß -unsaturated sulfoxides 206
5.6 Rearrangements Involving a,ß -unsaturated sulfoxides 230
5.7 Conclusion 236
References 236
Chapter 6. Preparation of Substituted 3-Sulfolenes and their use as Precursors for Diels–Alder Dienes 244
6.1 Introduction 244
6.2 Preparation of substituted 3-sulfolenes 245
6.3 Substitution reactions of sulfolenes 256
6.4 Formation of dienes from sulfolenes 275
6.5 Applications of substituted sulfolenes in Diels–Alder-based syntheses 287
6.6 Conclusion 304
References 304
Author Index 308
Subject Index 318