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.
Author(s): Olga Garcia-Mancheno
Publisher: Wiley-VCH
Year: 2022
Language: English
Pages: 416
City: Hoboken
Cover
Title Page
Copyright
Contents
Preface
List of Abbreviations
Chapter 1 From Anion Recognition to Organocatalytic Chemical Reactions
1.1 Introduction and Background
1.1.1 Evolution of Thiourea‐Based Catalysts
1.1.2 Evolution of Triazole‐Based Catalysts
1.1.3 Progress on Halogen‐Binding‐Based Catalysts
1.1.4 Miscellaneous Anion‐Binding Catalysts
1.2 Concepts in Anion‐Binding Catalysis
1.2.1 Introduction
1.2.2 Anion‐Binding Catalysis in Addition Reactions
1.2.3 Anion‐Binding Catalysis in Substitution Reactions
1.2.4 Anion Binding in Cooperative Catalysis
1.2.5 Anion‐Binding in Lewis Acid Enhancement Catalysis
1.2.6 Anion‐Binding in Phase Transfer Catalysis
1.3 Summary and Outlook
Acknowledgment
References
Chapter 2 Anion Recognition and Binding Constant Determination
2.1 Introduction to Supramolecular Chemistry and Binding Constant Determination
2.1.1 Chapter Overview
2.1.2 Supramolecular Chemistry and Its Connection to Anion‐Assisted Catalysis
2.1.3 Brief History of Advances in Supramolecular Anion Binding
2.1.4 Predicting the Model of Association and Simulating the Expected Species Distribution Profiles and Binding Curves
2.2 Equilibrium Constants, Binding Curves, Titration Conditions, and Errors
2.2.1 Physical Origins of Equilibrium Binding Constants
2.2.2 Explanation of the Basis for Titration Techniques and Binding Curves
2.2.3 Hirose's Rule and Picking the Right Concentration, Solvent, and Technique
2.2.4 Error Determination
2.3 Experimental Techniques: NMR Spectroscopy
2.3.1 When to Use
2.3.2 Slow Exchange vs. Fast Exchange
2.3.3 Determination of the Underlying Equilibria
2.3.4 Software for Non‐linear Regression Fitting
2.3.5 Common Issues
2.4 Experimental Techniques: UV–Vis Spectroscopy
2.4.1 When to Use
2.4.2 Physical Origins of Optical Phenomena
2.4.3 Software for Non‐linear Regression Analysis of UV–Vis Titrations
2.4.4 Common Issues
2.5 Underappreciated Concerns in Binding Constant Determination: Multiple Binding Equilibria
2.5.1 When to Expect Additional Equilibria
2.5.2 How to Diagnose Additional Equilibria
2.5.3 How to Account for Additional Equilibria
2.6 Underappreciated Concerns in Binding Constant Determination: Ion Pairing
2.6.1 When to Expect Ion Pairing
2.6.2 Role of Solvent and Concentration in Ion Pairing
2.6.3 How to Diagnose Ion Pairing
2.7 Underappreciated Concerns in Binding Constant Determination: Kinetic Processes
2.8 Connecting Equilibrium Constants to Structures and Catalysis
2.9 Conclusion
Acknowledgment
References
Chapter 3 (Thio)urea and Squaramide‐Catalyzed Anion‐Binding Catalysis with Halogen Anions
3.1 Introduction
3.2 History and Background
3.3 Asymmetric Catalysis by Catalyst Association with the Electrophile
3.3.1 Examples Utilizing the N‐Acyliminium Chloride Ion Pair
3.3.1.1 Pictet–Spengler Reaction and Variants
3.3.1.2 Intramolecular Cyclizations with Other (Hetero)aromatic Nucleophiles
3.3.1.3 Intramolecular and Intermolecular aza‐Sakurai Reaction
3.3.1.4 Mannich Reaction and Variants
3.3.1.5 Petasis‐Type Reactions
3.3.2 Examples Utilizing Electrophiles Other than N‐Acyliminium Ion Precursors
3.3.2.1 Utilization of Oxocarbenium and Pyrone Intermediates
3.3.2.2 Glycosylation Reactions Utilizing HBD–Halide Binding
3.3.2.3 Utilization of Non‐heteroatom‐Stabilized Carbocations as Electrophiles
3.4 Asymmetric Catalysis by Catalyst Association with the Nucleophile
3.4.1 Catalyst‐Nucleophile Association in Phase‐Transfer Catalysis
3.4.1.1 Investigation of Hydrogen‐Bonded Fluoride: Structure and Reactivity
3.4.1.2 Development of Hydrogen‐Bonding Phase‐Transfer Catalysis (HBPTC)
3.4.1.3 Development of Acyl‐Transfer Catalysis with Hydrogen‐Bonded Fluoride
3.4.2 Catalyst–Nucleophile Association in Homogeneous Catalysis
3.5 Conclusions and Outlook
Acknowledgments
References
Chapter 4 Chiral Ureas, Thioureas, and Squaramides in Anion‐Binding Catalysis with Co‐catalytic Brønsted/Lewis Acids
4.1 Introduction
4.2 Carboxylic Acid Co‐catalysts
4.3 Sulfonic Acid Co‐catalysts
4.4 Mineral Acid Co‐catalysts
4.5 Lewis Acid Co‐catalysts
4.6 Conclusions and Outlook
References
Chapter 5 Anion‐Binding Catalysis with Other Anions
5.1 Introduction
5.2 Cyanide Anion
5.2.1 Strecker Reaction
5.2.2 Acylcyanation of Imines
5.3 Oxygen‐Based Anions
5.3.1 Alkoxides and Enolates
5.3.2 Enolates of Lactones, Cyclic Anhydrides, and Imides
5.3.3 Carboxylates
5.4 Conclusions and Outlook
References
Chapter 6 Silanediols, Phosphoramides, and Other OH‐ and NH‐Based H‐Donor Catalysts
6.1 Introduction
6.2 Silanediols
6.2.1 Introduction
6.2.2 Overview of Silanols in Anion Binding and Catalysis
6.2.3 Silanediol Anion‐Binding Catalysis
6.2.4 Alkoxysilanediol Anion Binding Catalysis
6.3 Siloxanes
6.4 Thiophosphoramides
6.5 Cyclodiphosphazanes
6.6 Other Examples
6.6.1 Xanthene–Diamine Scaffold
6.6.2 Croconamides
6.6.3 Pyrrole‐Based Anion‐Binding Catalyst
6.6.4 Bisamidine Catalysts
6.7 Conclusions
References
Chapter 7 1,2,3‐Triazoles and 1,2,3‐Triazolium Ions as Catalysts
7.1 Introduction
7.2 Triazole‐Based Anion‐Binding Molecular Catalysts
7.3 Triazolium Ions as Organic Molecular Catalysts with Anion‐Binding Ability
7.4 Triazolium Ions in Dual Functional Catalysts
7.5 Conclusion
References
Chapter 8 Quaternary Ammonium, Phosphonium, and Tertiary Sulfonium Salts as Hydrogen‐Bonding Catalysts
8.1 Introduction
8.2 Hydrogen‐Bonding Ability of Quaternary Ammonium Salts
8.3 Hydrogen‐Bonding Catalysis of Quaternary Ammonium Salts
8.4 Hydrogen‐Bonding Catalysis of Quaternary Phosphonium Salts
8.5 Hydrogen‐Bonding Catalysis of Tertiary Sulfonium Salts
8.6 Conclusion
References
Chapter 9 Assisted and Dual Anion Binding in Amino and Nucleophilic Catalysis
9.1 Dual Amino/H‐Bond Donor Catalysis
9.1.1 Enamine Activation
9.1.2 Dienamine Activation
9.1.3 Iminium Ion Activation
9.1.4 Vinylogous Iminium Ion Activation
9.2 Thiourea – Pyridine‐Based Nucleophilic Dual Catalysis
9.2.1 Kinetic Resolution and Desymmetrization of Amines
9.2.2 Asymmetric Steglich Rearrangement
9.2.3 Other Acylation Reactions
9.2.4 Anion‐Binding‐Assisted Polymerization Reactions
9.3 Conclusions
References
Chapter 10 Anion‐Binding Catalysis by Halogen, Chalcogen, Pnictogen, and Tetrel Bonding
10.1 History of Halogen Bonding
10.2 History of Chalcogen Bonding
10.3 History of Pnictogen and Tetrel Bonding
10.4 Differences Between Hydrogen Bonding and Other Secondary Interactions
10.5 Secondary Bonding in Anion Recognition
10.6 Halogen Bonding in Anion‐Binding Catalysis
10.7 Chalcogen Bonding in Anion‐Binding Catalysis
10.8 Pnictogen and Tetrel Bonding in Anion‐Binding Catalysis
10.9 Conclusion
References
Chapter 11 New Trends and Supramolecular Approaches in Anion‐Binding Catalysis
11.1 General Introduction
11.2 Dual Photoredox and Anion‐Binding Catalysis
11.3 Combination of Metal and Anion‐Binding Catalysis
11.3.1 Anion‐Binding Assisted Hydrogenation Reactions
11.3.2 Hydroformylation Reactions
11.3.3 Anion‐Binding – Metal‐Catalyzed C–C Forming Reactions
11.4 Supramolecular Approaches Involving Anion‐Binding Catalysis
11.4.1 Mechanically Interlocked Molecules in Anion‐Binding Catalysis
11.4.1.1 Molecular Knots as Anion‐Binding Catalysts
11.4.1.2 Rotaxanes as Anion‐Binding Catalysts
11.4.2 Molecular Motors in Anion‐Binding Catalysis
11.4.3 Macrocycles in Anion‐Binding Catalysis
11.5 Anion–π Catalysis
11.5.1 Anion–π‐Catalyzed Kemp Elimination Reaction
11.5.2 Anion–π Interactions in Enolate Chemistry
11.5.3 Epoxide‐Opening – Ether Cyclization Reactions
11.5.4 Enantioselective Anion–π Catalysis
11.5.5 Miscellaneous
11.6 Conclusion and Outlook
References
Index
EULA
