Explores the potential of new types of anion-binding catalysts to solve challenging synthetic problems
Anion-Binding Catalysis introduces readers to the use of anion-binding processes in catalytic chemical activation, exploring how this approach can contribute to the future design of novel synthetic transformations. Featuring contributions by world-renowned scientists in the field, this authoritative volume describes the structure, properties, and catalytic applications of anions as well as synthetic applications and practical analytical methods.
In-depth chapters are organized by type of catalyst rather than reaction type, providing readers with an accessible overview of the existing classes of effective catalysts. The authors discuss the use of halogens as counteranions, the combination of (thio)urea and squaramide-based anion-binding with other types of organocatalysis, anion-binding catalysis by pnictogen and tetrel bonding, nucleophilic co-catalysis, anion-binding catalysis by pnictogen and tetrel bonding, and more. Helping readers appreciate and evaluate the potential of anion-binding catalysis, this timely book:
- Illustrates the historical development, activation mode, and importance of anion-binding in chemical catalysis
- Explains the analytic methods used to determine the anion-binding affinity of the catalysts
- Describes catalytic and synthetic applications of common NH- and OH-based hydrogen-donor catalysts as well as C-H triazole/triazolium catalysts
- Covers amino-catalysis involving enamine, dienamine, or iminium activation approaches
- Discusses new trends in the field of anion-binding catalysis, such as the combination of anion-binding with other types of catalysis
Presenting the current state of the field as well as the synthetic potential of anion-binding catalysis in future, Anion-Binding Catalysis is essential reading for researchers in both academia and industry involved in organic synthesis, homogeneous catalysis, and pharmaceutical chemistry.
Table of Contents
Preface xi
List of Abbreviations xiii
1 From Anion Recognition to Organocatalytic Chemical Reactions 1
Friedemann Dressler and Peter R. Schreiner
1.1 Introduction and Background 1
1.1.1 Evolution of Thiourea-Based Catalysts 10
1.1.2 Evolution of Triazole-Based Catalysts 22
1.1.3 Progress on Halogen-Binding-Based Catalysts 25
1.1.4 Miscellaneous Anion-Binding Catalysts 26
1.2 Concepts in Anion-Binding Catalysis 31
1.2.1 Introduction 31
1.2.2 Anion-Binding Catalysis in Addition Reactions 36
1.2.3 Anion-Binding Catalysis in Substitution Reactions 44
1.2.4 Anion Binding in Cooperative Catalysis 54
1.2.5 Anion-Binding in Lewis Acid Enhancement Catalysis 57
1.2.6 Anion-Binding in Phase Transfer Catalysis 59
1.3 Summary and Outlook 62
Acknowledgment 63
References 64
2 Anion Recognition and Binding Constant Determination 79
Edward G. Sheetz, David Van Craen, and Amar H. Flood
2.1 Introduction to Supramolecular Chemistry and Binding Constant Determination 79
2.1.1 Chapter Overview 79
2.1.2 Supramolecular Chemistry and Its Connection to Anion-Assisted Catalysis 80
2.1.3 Brief History of Advances in Supramolecular Anion Binding 84
2.1.4 Predicting the Model of Association and Simulating the Expected Species Distribution Profiles and Binding Curves 86
2.2 Equilibrium Constants, Binding Curves, Titration Conditions, and Errors 87
2.2.1 Physical Origins of Equilibrium Binding Constants 87
2.2.2 Explanation of the Basis for Titration Techniques and Binding Curves 88
2.2.3 Hirose’s Rule and Picking the Right Concentration, Solvent, and Technique 89
2.2.4 Error Determination 92
2.3 Experimental Techniques: NMR Spectroscopy 92
2.3.1 When to Use 92
2.3.2 Slow Exchange vs. Fast Exchange 93
2.3.3 Determination of the Underlying Equilibria 94
2.3.4 Software for Non-linear Regression Fitting 95
2.3.5 Common Issues 97
2.4 Experimental Techniques: UV-Vis Spectroscopy 97
2.4.1 When to Use 97
2.4.2 Physical Origins of Optical Phenomena 97
2.4.3 Software for Non-linear Regression Analysis of UV-Vis Titrations 98
2.4.4 Common Issues 99
2.5 Underappreciated Concerns in Binding Constant Determination: Multiple Binding Equilibria 99
2.5.1 When to Expect Additional Equilibria 99
2.5.2 How to Diagnose Additional Equilibria 100
2.5.3 How to Account for Additional Equilibria 101
2.6 Underappreciated Concerns in Binding Constant Determination: Ion Pairing 102
2.6.1 When to Expect Ion Pairing 102
2.6.2 Role of Solvent and Concentration in Ion Pairing 103
2.6.3 How to Diagnose Ion Pairing 103
2.7 Underappreciated Concerns in Binding Constant Determination: Kinetic Processes 104
2.8 Connecting Equilibrium Constants to Structures and Catalysis 104
2.9 Conclusion 105
Acknowledgment 105
References 105
3 (Thio)urea and Squaramide-Catalyzed Anion-Binding Catalysis with Halogen Anions 111
Matthew A. Horwitz and Véronique Gouverneur
3.1 Introduction 111
3.2 History and Background 111
3.3 Asymmetric Catalysis by Catalyst Association with the Electrophile 113
3.3.1 Examples Utilizing the N-Acyliminium Chloride Ion Pair 113
3.3.1.1 Pictet-Spengler Reaction and Variants 113
3.3.1.2 Intramolecular Cyclizations with Other (Hetero)aromatic Nucleophiles 115
3.3.1.3 Intramolecular and Intermolecular aza-Sakurai Reaction 116
3.3.1.4 Mannich Reaction and Variants 120
3.3.1.5 Petasis-Type Reactions 121
3.3.2 Examples Utilizing Electrophiles Other than N-Acyliminium Ion Precursors 123
3.3.2.1 Utilization of Oxocarbenium and Pyrone Intermediates 123
3.3.2.2 Glycosylation Reactions Utilizing HBD-Halide Binding 126
3.3.2.3 Utilization of Non-heteroatom-Stabilized Carbocations as Electrophiles 127
3.4 Asymmetric Catalysis by Catalyst Association with the Nucleophile 129
3.4.1 Catalyst-Nucleophile Association in Phase-Transfer Catalysis 130
3.4.1.1 Investigation of Hydrogen-Bonded Fluoride: Structure and Reactivity 130
3.4.1.2 Development of Hydrogen-Bonding Phase-Transfer Catalysis (HBPTC) 130
3.4.1.3 Development of Acyl-Transfer Catalysis with Hydrogen-Bonded Fluoride 134
3.4.2 Catalyst-Nucleophile Association in Homogeneous Catalysis 135
3.5 Conclusions and Outlook 136
Acknowledgments 137
References 137
4 Chiral Ureas, Thioureas, and Squaramides in Anion-Binding Catalysis with Co-catalytic Brønsted/Lewis Acids 141
Adam Trotta and Eric N. Jacobsen
4.1 Introduction 141
4.2 Carboxylic Acid Co-catalysts 141
4.3 Sulfonic Acid Co-catalysts 148
4.4 Mineral Acid Co-catalysts 152
4.5 Lewis Acid Co-catalysts 155
4.6 Conclusions and Outlook 157
References 157
5 Anion-Binding Catalysis with Other Anions 161
Sankash Mitra and Santanu Mukherjee
5.1 Introduction 161
5.2 Cyanide Anion 162
5.2.1 Strecker Reaction 163
5.2.2 Acylcyanation of Imines 168
5.3 Oxygen-Based Anions 169
5.3.1 Alkoxides and Enolates 169
5.3.2 Enolates of Lactones, Cyclic Anhydrides, and Imides 174
5.3.3 Carboxylates 182
5.4 Conclusions and Outlook 192
References 193
6 Silanediols, Phosphoramides, and Other OH- and NH-Based H-Donor Catalysts 201
Alexandria Leveille and Anita Mattson
6.1 Introduction 201
6.2 Silanediols 201
6.2.1 Introduction 201
6.2.2 Overview of Silanols in Anion Binding and Catalysis 202
6.2.3 Silanediol Anion-Binding Catalysis 203
6.2.4 Alkoxysilanediol Anion Binding Catalysis 207
6.3 Siloxanes 208
6.4 Thiophosphoramides 210
6.5 Cyclodiphosphazanes 213
6.6 Other Examples 215
6.6.1 Xanthene-Diamine Scaffold 215
6.6.2 Croconamides 216
6.6.3 Pyrrole-Based Anion-Binding Catalyst 217
6.6.4 Bisamidine Catalysts 217
6.7 Conclusions 218
References 218
7 1,2,3-Triazoles and 1,2,3-Triazolium Ions as Catalysts 221
Kohsuke Ohmatsu and Takashi Ooi
7.1 Introduction 221
7.2 Triazole-Based Anion-Binding Molecular Catalysts 224
7.3 Triazolium Ions as Organic Molecular Catalysts with Anion-Binding Ability 231
7.4 Triazolium Ions in Dual Functional Catalysts 240
7.5 Conclusion 241
References 242
8 Quaternary Ammonium, Phosphonium, and Tertiary Sulfonium Salts as Hydrogen-Bonding Catalysts 249
Seiji Shirakawa
8.1 Introduction 249
8.2 Hydrogen-Bonding Ability of Quaternary Ammonium Salts 249
8.3 Hydrogen-Bonding Catalysis of Quaternary Ammonium Salts 251
8.4 Hydrogen-Bonding Catalysis of Quaternary Phosphonium Salts 257
8.5 Hydrogen-Bonding Catalysis of Tertiary Sulfonium Salts 260
8.6 Conclusion 264
References 264
9 Assisted and Dual Anion Binding in Amino and Nucleophilic Catalysis 271
Efraim Reyes, Qui-Nhi Duong, Liher Prieto, Olga García Mancheño, and José L. Vicario
9.1 Dual Amino/H-Bond Donor Catalysis 271
9.1.1 Enamine Activation 272
9.1.2 Dienamine Activation 276
9.1.3 Iminium Ion Activation 278
9.1.4 Vinylogous Iminium Ion Activation 283
9.2 Thiourea - Pyridine-Based Nucleophilic Dual Catalysis 284
9.2.1 Kinetic Resolution and Desymmetrization of Amines 284
9.2.2 Asymmetric Steglich Rearrangement 290
9.2.3 Other Acylation Reactions 296
9.2.4 Anion-Binding-Assisted Polymerization Reactions 296
9.3 Conclusions 298
References 299
10 Anion-Binding Catalysis by Halogen, Chalcogen, Pnictogen, and Tetrel Bonding 307
Raffaella Papagna, Lukas Vogel, and Stefan M. Huber
10.1 History of Halogen Bonding 307
10.2 History of Chalcogen Bonding 310
10.3 History of Pnictogen and Tetrel Bonding 314
10.4 Differences Between Hydrogen Bonding and Other Secondary Interactions 315
10.5 Secondary Bonding in Anion Recognition 316
10.6 Halogen Bonding in Anion-Binding Catalysis 322
10.7 Chalcogen Bonding in Anion-Binding Catalysis 328
10.8 Pnictogen and Tetrel Bonding in Anion-Binding Catalysis 331
10.9 Conclusion 333
References 334
11 New Trends and Supramolecular Approaches in Anion-Binding Catalysis 345
María C. Pérez-Aguilar, Melania Gómez-Martínez, Jan Kuhlmann, and Olga García Mancheño
11.1 General Introduction 345
11.2 Dual Photoredox and Anion-Binding Catalysis 345
11.3 Combination of Metal and Anion-Binding Catalysis 351
11.3.1 Anion-Binding Assisted Hydrogenation Reactions 351
11.3.2 Hydroformylation Reactions 355
11.3.3 Anion-Binding - Metal-Catalyzed C-C Forming Reactions 358
11.4 Supramolecular Approaches Involving Anion-Binding Catalysis 359
11.4.1 Mechanically Interlocked Molecules in Anion-Binding Catalysis 359
11.4.1.1 Molecular Knots as Anion-Binding Catalysts 360
11.4.1.2 Rotaxanes as Anion-Binding Catalysts 363
11.4.2 Molecular Motors in Anion-Binding Catalysis 364
11.4.3 Macrocycles in Anion-Binding Catalysis 365
11.5 Anion-π Catalysis 368
11.5.1 Anion-π-Catalyzed Kemp Elimination Reaction 369
11.5.2 Anion-π Interactions in Enolate Chemistry 370
11.5.3 Epoxide-Opening - Ether Cyclization Reactions 372
11.5.4 Enantioselective Anion-π Catalysis 373
11.5.5 Miscellaneous 376
11.6 Conclusion and Outlook 376
References 377
Index 387
