Table Of ContentEdited by
Peter I. Dalko
Comprehensive Enantioselective
Organocatalysis
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Edited byPeter I. Dalko
Comprehensive Enantioselective
Organocatalysis
Catalysts, Reactions, and Applications
Volume 1: Privileged Catalysts
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V
Contents
Foreword XXVII
Preface XXIX
List of Contributors XXXI
Abbreviations XLI
Volume 1: Privileged Catalysts
Part I Amino Acid-Derived Catalysts 1
1 Proline-Related Secondary Amine Catalysts and Applications 3
Hiyoshizo Kotsuki and Niiha Sasakura
1.1 Introduction 3
1.2 Prolinamide and Related Catalysts 3
1.3 Prolinamine and Related Catalysts 8
1.4 Proline Tetrazole and Related Catalysts 10
1.5 Prolinamine Sulfonamide and Related Catalysts 13
1.6 Prolinamine Thiourea and Related Catalysts 15
1.7 Miscellaneous 16
1.8 Conclusions 21
Acknowledgments 21
References 21
2 TMS-Prolinol Catalyst in Organocatalysis 33
Hao Jiang, Łukasz Albrecht, Gustav Dickmeiss, Kim L. Jensen, and
Karl Anker Jørgensen
2.1 Introduction 33
2.2 Enamine Activation 34
2.3 Iminium-Ion Activation 37
2.4 Cascade Reactions 41
2.5 Dienamine Activation 42
2.6 Trienamine Activation 46
2.7 Summary and Conclusions 48
References 48
VI Contents
3 Non-Proline Amino Acid Catalysts 51
Li-Wen Xu and Yixin Lu
3.1 Introduction 51
3.2 Primary Amino Acids in Amino Catalysis 52
3.3 Primary Amino Acid-Derived Organic Catalysts 53
3.3.1 Unmodified Amino Acids 55
3.3.2 Protected Primary Amino Acids 55
3.3.3 Primary Amino Acid-Derived Diamine Catalysts 55
3.3.4 Other Primary Amino Acid Catalysts 55
3.4 Applications of Non-Proline Primary Amino Acid Catalysts 56
3.4.1 Aldol Reaction 56
3.4.2 Mannich Reaction 60
3.4.3 Michael Addition 62
3.4.4 Other Reactions 64
3.5 Conclusions 65
Acknowledgments 66
References 66
4 Chiral Imidazolidinone (MacMillan’s) Catalyst 69
Rainer Mahrwald
4.1 Introduction 69
4.2 Enamine Catalysis 69
4.3 Iminium Catalysis 81
4.4 Cascade Reaction – Merging Iminium and Enamine Catalysis 86
References 91
5 Oligopeptides as Modular Organocatalytic Scaffolds 97
Roberto Fanelli and Umberto Piarulli
5.1 Introduction 97
5.2 C–C Bond Forming Reactions 98
5.2.1 Aldol Reactions 98
5.2.2 Michael Reactions 101
5.2.3 Morita–Baylis–Hillman Reactions 105
5.2.4 Hydrocyanation of Aldehydes 107
5.3 Asymmetric Acylations 108
5.4 Asymmetric Phosphorylations 110
5.5 Enantioselective Oxidations 111
5.6 Hydrolytic Reactions 114
5.7 Summary and Conclusions 114
References 114
Contents VII
Part II Non-Amino Acid-Derived Catalysts 117
6 Cinchonas and Cupreidines 119
Steen Ingemann and Henk Hiemstra
6.1 Introduction 119
6.2 Cinchona Alkaloid Derivatives 120
6.3 Natural Cinchona Alkaloids, Cupreine, and Cupreidine 121
6.3.1 Structural Properties 121
6.3.2 Catalysis with Natural Cinchona Alkaloids 122
6.3.3 Catalysis with Cupreine and Cupreidine 125
6.4 Cinchona Alkaloids with an Ether or Ester Group at C9 127
6.4.1 Structural Properties 127
6.4.2 Catalysis with C9 Ethers of Natural Cinchona Alkaloids 127
6.4.3 Catalysis with C9 Ethers of Cupreine and Cupreidine 129
6.4.4 Catalysis with C9 Esters 133
6.5 Cinchona Alkaloid Derivatives with a Sulfonamide, Urea, Thiourea,
Squaramide, or Guanidine Function 134
6.5.1 Structural Properties 134
6.5.2 Catalysis with C9 and C6′ Thiourea Derivatives 136
6.5.3 Catalysis with C9 Sulfonamide, Squaramide, and Guanidine
Derivatives 141
6.6 Cinchona Alkaloids with a Primary Amine Group at C9 145
6.6.1 Structural Properties 145
6.6.2 Catalysis with C9 Amino Derivatives 146
6.7 Cinchona Alkaloids in Phase-Transfer Catalysis 149
6.8 Ether Bridged Dimers 151
6.9 Some Novel Cinchona Alkaloid Derivatives 153
6.10 Prospects 154
References 155
7 Chiral C Catalysts 161
2
Daisuke Uraguchi, Kohsuke Ohmatsu, and Takashi Ooi
7.1 Introduction 161
7.2 Chiral Lewis Base Catalysts 161
7.2.1 Phosphoramides 162
7.2.2 Bipyridine N,N′-Dioxides 167
7.2.3 Bisphosphine Dioxides 169
7.3 Phosphines 172
7.4 Chiral C-Symmetric Secondary and Primary Amines 174
2
7.5 Chiral C-Symmetric Brønsted Bases: Guanidines 177
2
7.6 Chiral C-Symmetric Brønsted Acids 181
2
7.6.1 Binaphthol and Biphenol Derivatives 181
7.6.2 Pyridinium Disulfonates 182
7.6.3 Dicarboxylic Acids 183
7.6.4 Chiral Disulfonimides 186
VIII Contents
7.7 Chiral C-Symmetric Bis-Thioureas 188
2
7.8 Chiral C-Symmetric Aminophosphonium Ions 189
2
7.9 Summary and Conclusions 190
References 190
8 Planar Chiral Catalysts 195
Olivier R.P. David
8.1 Introduction 195
8.2 Lewis/Brønsted Bases 198
8.2.1 Nitrogen Bases 198
8.2.1.1 Azaferrocenes 199
8.2.1.2 Pyridinoferrocenes 200
8.2.1.3 Imidazoles 204
8.2.1.4 PIP: Paracyclophane-2,3-dihydroimidazolo[1,2-a]pyridine Bases 204
8.2.1.5 Imine 205
8.2.2 Oxygen Lewis Bases 206
8.2.3 Phosphine 207
8.2.4 N-Heterocyclic Carbenes 209
8.2.5 Sulfides 210
8.3 Lewis/Brønsted Acids 211
8.3.1 Boronic Acids 211
8.3.2 Phenols 212
8.3.3 Thioureas 212
8.4 Redox Reactions 213
8.4.1 Flavin Derivatives 213
8.4.2 Hantzsch Esters 214
8.5 Summary and Conclusions 214
References 215
9 Dynamic Approaches towards Catalyst Discovery 221
Patrizia Galzerano, Giulio Gasparini, Marta Dal Molin, and
Leonard J. Prins
9.1 Introduction 221
9.2 Self-Assembly 222
9.2.1 Self-Assembled Organocatalysts 223
9.2.2 Catalysis in Confined Self-Assembled Space 227
9.3 Self-Selected Catalysts 232
9.3.1 Dynamic Combinatorial Chemistry 232
9.4 Conclusions 236
Acknowledgments 236
References 236
Appendix A1
