Chiral Ligands: Evolution of Ligand Libraries for Asymmetric Catalysis

Description

Many new drugs on the market are chiral compounds, that is, they can exist in two non-superimposable mirror-image forms. Asymmetric catalysis encompasses a large variety of processes for obtaining such compounds. The performance of the catalyst in those processes largely depends on the ligand that makes up the catalyst. This book describes the most relevant ligand libraries for some key processes, including an overview of the state of art and the key mechanistic aspects that favor a high catalytic performance. Cover Half Title Series Page Title Page Copyright Page Table of Contents Preface Editor List of Contributors Abbreviations and Acronyms Chapter 1 Chiral Bidentate Heterodonor P-Oxazoline Ligands 1.1 Introduction 1.2 Application of Bidentate Heterodonor P-Oxazoline Ligands in Asymmetric Catalytic Transformations 1.3 Conclusions 1.4 Acknowledgements References Chapter 2 Chiral Bidentate Heterodonor P-N-Other-Ligands 2.1 Introduction 2.2 Properties of P,N-Ligands 2.3 Structure-Performance Characteristics of P,N-Ligands 2.3.1 Group 1: P,N-Amino Ligands 2.3.1.1 Diphenylphosphinoferrocenylamine (PPFA) and Analogs 2.3.1.2 β-Aminoalkylphosphines 2.3.1.3 Diarylphosphino-1,1’-Binaphthyl Amines (MAP Family) 2.3.1.4 Spiranic Ligands 2.3.1.5 Cinchona-Derived Ligands 2.3.2 Group 2: P,N-Imino Ligands 2.3.2.1 Ferrocenylphosphine-Imino Ligands 2.3.2.2 α-Phosphino-β-Imine-Arene Ligands 2.3.2.3 Phosphinosulfoximine Ligands 2.3.3 Group 3: P,N-Cyclic Imino Ligands 2.3.3.1 Phosphinyl Oxazole- and Thiazole-Based Ligands 2.3.3.2 Phosphinyl Imidazole-Based Ligands 2.3.3.3 Phosphinyl Imidazoline-Based Ligands 2.3.4 Group 4: P,N-Pyridino Ligands 2.3.4.1 Phosphino-Pyridine and Terpene-Based P,N-Pyridino Ligands 2.3.4.2 Pfaltz’s Phosphine- and Phosphinite-Pyridines 2.3.4.3 Phosphite-Pyridine Ligands 2.3.4.4 BoQPhos and Aminophosphine Pyridine Ligands 2.3.4.5 Axially Chiral P,N-Pyridino Ligands 2.3.4.6 Phosphino-Amidopyridine Ligands 2.3.4.7 Binepine–Pyridyl Ligands 2.4 Conclusions 2.5 Acknowledgments Bibliography Chapter 3 Chiral Bidentate Heterodonor P,S/O Ligands 3.1 Introduction 3.2 Application of Heterodonor P,O Ligands in Asymmetric Catalysis 3.3 Application of Heterodonor P,S Ligands in Asymmetric Catalysis 3.4 Conclusions 3.5 Acknowledgements References Chapter 4 Chiral Bidentate Heterodonor P-P’ ligands 4.1 Historical Perspective 4.2 General Features of Heterodonor P-P’ Ligands 4.2.1 Electronic properties 4.2.2 C2 vs C1 ligand symmetry 4.3 Synthesis and Catalytic Applications of Bidentate Heterodonor P-P’ Ligands 4.3.1 P-P’ Diphosphines 4.3.1.1 Synthesis and Structure 4.3.1.2 Catalytic applications 4.3.2 Phosphine-Aminophosphines 4.3.2.1 Synthesis 4.3.2.2 Catalytic Applications 4.3.3 Phosphine-Phosphonites and Phosphine-Phosphinites 4.3.4 Phosphine-Phosphoramidites 4.3.4.1 Synthesis 4.3.4.2 Catalytic applications 4.3.5 Phosphine-Phosphites 4.3.5.1 Synthesis 4.3.5.2 Catalytic applications 4.4 Concluding remarks Acknowledgment References Chapter 5 Chiral Tridentate-Based Ligands 5.1 Introduction 5.2 NNN Ligands 5.3 PNN Ligands 5.4 NPN Ligands 5.5 PNP Ligands 5.6 PNS Ligands 5.7 NNO Ligands 5.7.1 Pseudodipeptide Ligands 5.7.2 Other NNO Ligands 5.8 ONO Ligands 5.9 NCN Ligands 5.10 Conclusion References Chapter 6 Chiral N-Heterocyclic Carbene-Based Ligands 6.1 Introduction 6.2 Monodentate Chiral NHC Ligands 6.2.1 Monodentate NHC Ligands with Chiral Exocyclic Nitrogen Substituents 6.2.1.1 With an Asymmetric Carbon Atom in α-Position to the N-Atoms 6.2.1.2 With C2-Symmetric, Chiral Ortho-Disubstituted Aryl Groups 6.2.2 Monodentate NHC Ligands with a Chiral Heterocyclic Backbone 6.2.3 Monodentate Chiral Polycyclic NHC Ligands 6.2.4 Perspectives and New Trends/Directions 6.3 Polyfunctional Chiral NHC Ligands 6.3.1 Polyfunctional Chiral NHC-N, NHC-P, and NHC-S Ligands 6.3.2 Polyfunctional Chiral NHC-C Ligands 6.3.3 Polyfunctional Chiral NHC-O Ligands 6.3.3.1 Polyfunctional Chiral NHC-Aryl/alkoxide Ligands 6.3.3.2 Polyfunctional Chiral NHC-Sulfonate Ligands 6.3.3.3 Summary and Future Trends 6.4 Conclusion References Chapter 7 Chiral Monophosphorus Ligands 7.1 Introduction 7.2 Asymmetric Allylic Substitution 7.2.1 Asymmetric Dearomative Allylation 7.2.2 Asymmetric Allylic Substitution with Other Carbon Nucleophiles 7.2.3 Asymmetric Allylic Substitution with Heteroatom Nucleophiles 7.2.4 Pd-Catalyzed Cyclization Based on Allylic Chemistry 7.3 Asymmetric Dearomative and Heck-Type Cyclization 7.4 Asymmetric Cross-Coupling Reaction 7.5 Asymmetric C–H Bond Functionalization 7.6 Asymmetric Coupling of π-Systems Catalyzed by Transition Metals 7.7 Asymmetric Addition 7.8 Asymmetric Hydrogenation 7.9 Conclusions and Outlook References Chapter 8 Solvent-Oriented Ligand and Catalyst Design in Asymmetric Catalysis – Principles and Limits 8.1 Introduction 8.2 Properties of Solvents and Solvent-Oriented Ligand Design 8.2.1 General Considerations 8.2.2 Mixtures of Miscible Solvents 8.2.3 Mixtures of Non-Miscible Solvents 8.2.4 Temperature-Dependent Multicomponent Solvent Systems (TMS) 8.2.5 Solvent-Dependent a Posteriori Separation of Catalyst and Product 8.2.6 Special Solvent Effects in Homogeneous Catalysis 8.3 Unusual Solvents – Applications 8.3.1 Reactions in Ionic Liquids (ILs) 8.3.2 Supercritical Fluents (SCFs) in the scCO2 Example 8.3.3 Propylene Carbonate (PC) and Other Organic Carbonates 8.3.4 Fluorinated alcohols 8.3.5 Water as Solvent 8.3.5.1 Phosphorus Ligands Decorated with Sulfonic Acids 8.3.5.2 Phosphines with Hydroxyl Functionalities 8.3.6 Chiral Solvents 8.4 Conclusions References Index