This book introduces multi-catalyst systems by describing their
mechanism and advantages in asymmetric catalysis.
* Helps organic chemists perform more efficient
catalysis with step-by-step methods
* Overviews new concepts and progress for greener and
economic catalytic reactions
* Covers topics of interest in asymmetric catalysis
including bifunctional catalysis, cooperative catalysis,
multimetallic catalysis, and novel tandem reactions
* Has applications for pharmaceuticals, agrochemicals,
materials, and flavour and fragrance
Autorentext
Jian Zhou is a Professor of Chemistry in the Shanghai Key
Laboratory of Green Chemistry and Chemical Processes at East China
Normal University. He has broad experience in asymmetric catalysis
and has published over 30 papers in leading scientific journals
after his independent research. Dr. Zhou's research focuses
on the development of new chiral catalysts and catalytic asymmetric
reactions for the efficient construction of fully substituted
stereogenic carbon centres, as well as economical synthesis and
novel tandem reactions.
Zusammenfassung
This book introduces multi-catalyst systems by describing their mechanism and advantages in asymmetric catalysis.
• Helps organic chemists perform more efficient catalysis with step-by-step methods
• Overviews new concepts and progress for greener and economic catalytic reactions
• Covers topics of interest in asymmetric catalysis including bifunctional catalysis, cooperative catalysis, multimetallic catalysis, and novel tandem reactions
• Has applications for pharmaceuticals, agrochemicals, materials, and flavour and fragrance
Inhalt
Preface xi
Contributors xiv
1 Toward Ideal Asymmetric Catalysis 1
Jian Zhou and Jin-Sheng Yu
1.1 Introduction 1
1.2 Challenges to Realize Ideal Asymmetric Catalysis 7
1.3 Solutions 13
1.4 Borrow Ideas from Nature 22
1.5 Conclusion 32
References 32
2 Multicatalyst System 37
Zhong-Yan Cao Feng Zhu and Jian Zhou
2.1 Introduction 37
2.2 Models of Substrate Activation 42
2.2.1 The Activation of Electrophiles 43
2.2.2 The Activation of Nucleophiles 54
2.2.3 SOMO Catalysis 64
2.3 Early Examples of the Application of Multicatalyst System in Asymmetric Catalysis 66
2.4 A General Introduction of Multicatalyst-Promoted Asymmetric Reactions 85
2.5 Classification of Multicatalyst-Promoted Asymmetric Reactions 95
2.6 Challenges and Possible Solutions 97
2.7 Multicatalyst System Versus Multifunctional Catalyst 103
2.8 Multicatalyst System Versus Additives-Enhanced Catalysis 105
2.9 Additive-Enhanced Catalysis 107
2.9.1 Nitrogen-containing Organobase 109
2.9.2 Inorganic Bases 111
2.9.3 H2O 114
2.9.4 Molecular Sieves and Dehydrators 120
2.9.5 N-oxide P-oxide and As-oxide 125
2.9.6 Alcohols and Phenols 129
2.9.7 Ammonium Halides and Metal Halides 133
2.9.8 Amides 137
2.9.9 Brønsted Acids and Lewis Acids 140
2.9.10 Two or More Additives Together 144
2.10 Conclusion 147
References 148
3 Asymmetric Multifunctional Catalysis 159
Jin-Sheng Yu and Jian Zhou
3.1 Introduction 159
3.2 Asymmetric Multifunctional Organocatalysis 164
3.2.1 H-Bond DonorTertiary Amine Catalysis 165
3.2.2 H-Bond DonorEnamine Catalysis 193
3.2.3 H-Bond DonorPhase Transfer Catalysis 203
3.2.4 H-Bond DonorTertiary Phosphine Catalysis 209
3.2.5 Chiral Phosphoric Acid Catalysis 214
3.2.6 Asymmetric Bifunctional Salt Catalysis 217
3.2.7 Miscellaneous 222
3.3 Asymmetric Hybrid Organo/Metal Catalysis 227
3.3.1 Brønsted Base/Lewis Acid Bifunctional Catalysis 228
3.3.2 Lewis Base/Lewis Acid Bifunctional Catalysis 233
3.3.3 Brønsted Acid/Lewis Acid Bifunctional Catalysis 236
3.3.4 Enamine/Lewis Acid Bifunctional Catalysis 238
3.3.5 Hemilable Trisoxazolines 240
3.4 Asymmetric Multifunctional Multimetallic Catalysis 242
3.4.1 Asymmetric Multifunctional Heteromultimetallic Catalysis 243
3.4.2 Asymmetric Multifunctional Homomultimetallic Catalysis 251
3.5 Anion-Enabled Bifunctional Asymmetric Catalysis 259
3.5.1 Ammonium Fluorides or Metal Fluorides 262
3.5.2 Metal Phosphates 265
3.5.3 Metal Carboxylates 265
3.5.4 Ammonium or Metal Aryloxides 269
3.5.5 Hydroxides and Alkoxides 271
3.5.6 Metal Amides 276
3.6 Conclusion 277
References 277
4 Asymmetric Cooperative Catalysis 291
Long Chen Yun-Lin Liu and Jian Zhou
4.1 Introduction 291
4.2 Catalytic Asymmetric Michael Addition Reaction 292
4.2.1 Combining Multiple Metal Catalysts 292
4.2.2 Combining Two Distinct Organocatalysts 293
4.2.3 Combining Metal Catalyst with Organocatalyst 297
4.3 Catalytic Asymmetric Mannich Reaction 299
4.3.1 Combining Lewis Acid Catalyst and Brønsted Base Catalyst 300
4.3.2 Combining Brønsted Acid Catalyst and Lewis Acid Catalyst 301
4.3.3 Combining Brønsted Acid Catalyst and Secondary Amine Catalyst 303
4.4 Catalytic Asymmetric Conia-Ene Reaction 304
4.4.1 Combining Chiral Lewis Acid and Achiral Lewis Acid 304
4.4.2 Combining Chiral Brønsted Base and Achiral Lewis Acid 306
4.5 Catalytic Asymmetric Umpolung Reaction 307
4.5.1 Combining NHC Catalyst and Lewis Acid Catalyst 307
4.5.2 Combining NHC Catalyst and Brønsted Acid Catalyst 313
4.6 Catalytic Asymmetric Cyanosilylation Reacti...