Anion-Binding Catalysis

**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. Cover 1 Title Page 5 Copyright 6 Contents 7 Preface 13 List of Abbreviations 15 Chapter 1 From Anion Recognition to Organocatalytic Chemical Reactions 19 1.1 Introduction and Background 19 1.1.1 Evolution of Thiourea‐Based Catalysts 28 1.1.2 Evolution of Triazole‐Based Catalysts 40 1.1.3 Progress on Halogen‐Binding‐Based Catalysts 43 1.1.4 Miscellaneous Anion‐Binding Catalysts 44 1.2 Concepts in Anion‐Binding Catalysis 49 1.2.1 Introduction 49 1.2.2 Anion‐Binding Catalysis in Addition Reactions 54 1.2.3 Anion‐Binding Catalysis in Substitution Reactions 62 1.2.4 Anion Binding in Cooperative Catalysis 72 1.2.5 Anion‐Binding in Lewis Acid Enhancement Catalysis 75 1.2.6 Anion‐Binding in Phase Transfer Catalysis 77 1.3 Summary and Outlook 80 Acknowledgment 81 References 82 Chapter 2 Anion Recognition and Binding Constant Determination 97 2.1 Introduction to Supramolecular Chemistry and Binding Constant Determination 97 2.1.1 Chapter Overview 97 2.1.2 Supramolecular Chemistry and Its Connection to Anion‐Assisted Catalysis 98 2.1.3 Brief History of Advances in Supramolecular Anion Binding 102 2.1.4 Predicting the Model of Association and Simulating the Expected Species Distribution Profiles and Binding Curves 104 2.2 Equilibrium Constants, Binding Curves, Titration Conditions, and Errors 105 2.2.1 Physical Origins of Equilibrium Binding Constants 105 2.2.2 Explanation of the Basis for Titration Techniques and Binding Curves 106 2.2.3 Hirose's Rule and Picking the Right Concentration, Solvent, and Technique 107 2.2.4 Error Determination 110 2.3 Experimental Techniques: NMR Spectroscopy 110 2.3.1 When to Use 110 2.3.2 Slow Exchange vs. Fast Exchange 111 2.3.3 Determination of the Underlying Equilibria 112 2.3.4 Software for Non‐linear Regression Fitting 113 2.3.5 Common Issues 115 2.4 Experimental Techniques: UV–Vis Spectroscopy 115 2.4.1 When to Use 115 2.4.2 Physical Origins of Optical Phenomena 115 2.4.3 Software for Non‐linear Regression Analysis of UV–Vis Titrations 116 2.4.4 Common Issues 117 2.5 Underappreciated Concerns in Binding Constant Determination: Multiple Binding Equilibria 117 2.5.1 When to Expect Additional Equilibria 117 2.5.2 How to Diagnose Additional Equilibria 118 2.5.3 How to Account for Additional Equilibria 119 2.6 Underappreciated Concerns in Binding Constant Determination: Ion Pairing 120 2.6.1 When to Expect Ion Pairing 120 2.6.2 Role of Solvent and Concentration in Ion Pairing 121 2.6.3 How to Diagnose Ion Pairing 121 2.7 Underappreciated Concerns in Binding Constant Determination: Kinetic Processes 122 2.8 Connecting Equilibrium Constants to Structures and Catalysis 122 2.9 Conclusion 123 Acknowledgment 123 References 123 Chapter 3 (Thio)urea and Squaramide‐Catalyzed Anion‐Binding Catalysis with Halogen Anions 129 3.1 Introduction 129 3.2 History and Background 129 3.3 Asymmetric Catalysis by Catalyst Association with the Electrophile 131 3.3.1 Examples Utilizing the N‐Acyliminium Chloride Ion Pair 131 3.3.1.1 Pictet–Spengler Reaction and Variants 131 3.3.1.2 Intramolecular Cyclizations with Other (Hetero)aromatic Nucleophiles 133 3.3.1.3 Intramolecular and Intermolecular aza‐Sakurai Reaction 134 3.3.1.4 Mannich Reaction and Variants 138 3.3.1.5 Petasis‐Type Reactions 139 3.3.2 Examples Utilizing Electrophiles Other than N‐Acyliminium Ion Precursors 141 3.3.2.1 Utilization of Oxocarbenium and Pyrone Intermediates 141 3.3.2.2 Glycosylation Reactions Utilizing HBD–Halide Binding 144 3.3.2.3 Utilization of Non‐heteroatom‐Stabilized Carbocations as Electrophiles 145 3.4 Asymmetric Catalysis by Catalyst Association with the Nucleophile 147 3.4.1 Catalyst‐Nucleophile Association in Phase‐Transfer Catalysis 148 3.4.1.1 Investigation of Hydrogen‐Bonded Fluoride: Structure and Reactivity 148 3.4.1.2 Development of Hydrogen‐Bonding Phase‐Transfer Catalysis (HBPTC) 148 3.4.1.3 Development of Acyl‐Transfer Catalysis with Hydrogen‐Bonded Fluoride 152 3.4.2 Catalyst–Nucleophile Association in Homogeneous Catalysis 153 3.5 Conclusions and Outlook 154 Acknowledgments 155 References 155 Chapter 4 Chiral Ureas, Thioureas, and Squaramides in Anion‐Binding Catalysis with Co‐catalytic Brønsted/Lewis Acids 159 4.1 Introduction 159 4.2 Carboxylic Acid Co‐catalysts 159 4.3 Sulfonic Acid Co‐catalysts 166 4.4 Mineral Acid Co‐catalysts 170 4.5 Lewis Acid Co‐catalysts 173 4.6 Conclusions and Outlook 175 References 175 Chapter 5 Anion‐Binding Catalysis with Other Anions 179 5.1 Introduction 179 5.2 Cyanide Anion 180 5.2.1 Strecker Reaction 181 5.2.2 Acylcyanation of Imines 186 5.3 Oxygen‐Based Anions 187 5.3.1 Alkoxides and Enolates 187 5.3.2 Enolates of Lactones, Cyclic Anhydrides, and Imides 192 5.3.3 Carboxylates 200 5.4 Conclusions and Outlook 210 References 211 Chapter 6 Silanediols, Phosphoramides, and Other OH‐ and NH‐Based H‐Donor Catalysts 219 6.1 Introduction 219 6.2 Silanediols 219 6.2.1 Introduction 219 6.2.2 Overview of Silanols in Anion Binding and Catalysis 220 6.2.3 Silanediol Anion‐Binding Catalysis 221 6.2.4 Alkoxysilanediol Anion Binding Catalysis 225 6.3 Siloxanes 226 6.4 Thiophosphoramides 228 6.5 Cyclodiphosphazanes 231 6.6 Other Examples 233 6.6.1 Xanthene–Diamine Scaffold 233 6.6.2 Croconamides 234 6.6.3 Pyrrole‐Based Anion‐Binding Catalyst 235 6.6.4 Bisamidine Catalysts 235 6.7 Conclusions 236 References 236 Chapter 7 1,2,3‐Triazoles and 1,2,3‐Triazolium Ions as Catalysts 239 7.1 Introduction 239 7.2 Triazole‐Based Anion‐Binding Molecular Catalysts 242 7.3 Triazolium Ions as Organic Molecular Catalysts with Anion‐Binding Ability 249 7.4 Triazolium Ions in Dual Functional Catalysts 258 7.5 Conclusion 259 References 260 Chapter 8 Quaternary Ammonium, Phosphonium, and Tertiary Sulfonium Salts as Hydrogen‐Bonding Catalysts 267 8.1 Introduction 267 8.2 Hydrogen‐Bonding Ability of Quaternary Ammonium Salts 267 8.3 Hydrogen‐Bonding Catalysis of Quaternary Ammonium Salts 269 8.4 Hydrogen‐Bonding Catalysis of Quaternary Phosphonium Salts 275 8.5 Hydrogen‐Bonding Catalysis of Tertiary Sulfonium Salts 278 8.6 Conclusion 282 References 282 Chapter 9 Assisted and Dual Anion Binding in Amino and Nucleophilic Catalysis 289 9.1 Dual Amino/H‐Bond Donor Catalysis 289 9.1.1 Enamine Activation 290 9.1.2 Dienamine Activation 294 9.1.3 Iminium Ion Activation 296 9.1.4 Vinylogous Iminium Ion Activation 301 9.2 Thiourea – Pyridine‐Based Nucleophilic Dual Catalysis 302 9.2.1 Kinetic Resolution and Desymmetrization of Amines 302 9.2.2 Asymmetric Steglich Rearrangement 308 9.2.3 Other Acylation Reactions 314 9.2.4 Anion‐Binding‐Assisted Polymerization Reactions 314 9.3 Conclusions 316 References 317 Chapter 10 Anion‐Binding Catalysis by Halogen, Chalcogen, Pnictogen, and Tetrel Bonding 325 10.1 History of Halogen Bonding 325 10.2 History of Chalcogen Bonding 328 10.3 History of Pnictogen and Tetrel Bonding 332 10.4 Differences Between Hydrogen Bonding and Other Secondary Interactions 333 10.5 Secondary Bonding in Anion Recognition 334 10.6 Halogen Bonding in Anion‐Binding Catalysis 340 10.7 Chalcogen Bonding in Anion‐Binding Catalysis 346 10.8 Pnictogen and Tetrel Bonding in Anion‐Binding Catalysis 349 10.9 Conclusion 351 References 352 Chapter 11 New Trends and Supramolecular Approaches in Anion‐Binding Catalysis 363 11.1 General Introduction 363 11.2 Dual Photoredox and Anion‐Binding Catalysis 363 11.3 Combination of Metal and Anion‐Binding Catalysis 369 11.3.1 Anion‐Binding Assisted Hydrogenation Reactions 369 11.3.2 Hydroformylation Reactions 373 11.3.3 Anion‐Binding – Metal‐Catalyzed C–C Forming Reactions 376 11.4 Supramolecular Approaches Involving Anion‐Binding Catalysis 377 11.4.1 Mechanically Interlocked Molecules in Anion‐Binding Catalysis 377 11.4.1.1 Molecular Knots as Anion‐Binding Catalysts 378 11.4.1.2 Rotaxanes as Anion‐Binding Catalysts 381 11.4.2 Molecular Motors in Anion‐Binding Catalysis 382 11.4.3 Macrocycles in Anion‐Binding Catalysis 383 11.5 Anion–π Catalysis 386 11.5.1 Anion–π‐Catalyzed Kemp Elimination Reaction 387 11.5.2 Anion–π Interactions in Enolate Chemistry 388 11.5.3 Epoxide‐Opening – Ether Cyclization Reactions 390 11.5.4 Enantioselective Anion–π Catalysis 391 11.5.5 Miscellaneous 394 11.6 Conclusion and Outlook 394 References 395 Index 405 EULA 416 Front Matter -- From Anion Recognition to Organocatalytic Chemical Reactions / Friedemann Dressler, Peter R. Schreiner -- Anion Recognition and Binding Constant Determination / Edward G Sheetz, David Van Craen, Amar H Flood -- (Thio)urea and Squaramide-Catalyzed Anion-Binding Catalysis with Halogen Anions / Matthew A Horwitz, Veronique Gouvenour -- Chiral Ureas, Thioureas, and Squaramides in Anion-Binding Catalysis with Co-catalytic Bronsted/Lewis Acids / Adam Trotta, Eric N Jacobsen -- Anion-Binding Catalysis with Other Anions / Sankash Mitra, Santanu Mukherjee -- Silanediols, Phosphoramides, and Other OH- and NH-Based H-Donor Catalysts / Alexandria Leveille, Anita Mattson -- 1,2,3-Triazoles and 1,2,3-Triazolium Ions as Catalysts / Kohsuke Ohmatsu, Takashi Ooi -- Quaternary Ammonium, Phosphonium, and Tertiary Sulfonium Salts as Hydrogen-Bonding Catalysts / Seiji Shirakawa -- Assisted and Dual Anion Binding in Amino and Nucleophilic Catalysis / Efraim Reyes, Qui-Nhi Duong, Liher Prieto, Olga Garcia Mancheno, Jose L Vicario -- Anion-Binding Catalysis by Halogen, Chalcogen, Pnictogen, and Tetrel Bonding / Raffaella Papagna, Lukas Vogel, Stefan M Huber -- New Trends and Supramolecular Approaches in Anion-Binding Catalysis / Maria C Perez-Aguilar, Melania Gomez-Martinez, Jan Kuhlmann, Olga Garcia Mancheno