Chirality in Supramolecular Assemblies: Causes and Consequences

Table of Contents:
List of Contributors xi Preface xiii 1 Principles of Molecular Chirality 1 Jean?]Claude Chambron and F. Richard Keene 1.1 General Introduction 1 1.2 Geometrical Chirality 2 1.3 Topological Chirality 25 1.4 Conclusion 39 References 39 2 Homochirogenesis and the Emergence of Lifelike Structures 44 Pedro Cintas 2.1 Introduction and Scope 44 2.2 The Racemic State: Mirror Symmetry Breaking 45 2.3 Asymmetric Oligomerization 49 2.4 Biochirality in Active Sites 58 2.5 Conclusions 61 Acknowledgements 61 References 61 3 Aspects of Crystallization and Chirality 65 Roger Bishop 3.1 Introduction 65 3.2 Crystal Space Groups 65 3.3 Fundamentals of Crystallization for a Racemic Mixture 69 3.4 More Complex Crystallization Behavior 71 3.5 Multiple Crystal Forms 74 3.6 Conglomerates Revisited 85 References 90 4 Complexity of Supramolecular Assemblies 94 Jonathan A. Kitchen and Philip A. Gale 4.1 Introduction 94 4.2 Generating Supramolecular Chirality through Assembly of Achiral Components 96 4.3 Enantioselective Supramolecular Assemblies 121 4.4 Conclusions and Future Outlook 134 References 134 5 Chirality in the Host?]Guest Behaviour of Supramolecular Systems 142 Nicholas H. Evans and Paul D. Beer 5.1 An Introduction to Chiral Recognition and its Importance 142 5.2 Chiral Hosts for Chiral Guests 143 5.3 Conclusions: Summary and Future Directions 155 References 156 6 Chiral Influences in Functional Molecular Materials 159 David B. Amabilino 6.1 Introduction 159 6.2 Functional Molecular Materials in Different States 161 6.3 Switching 168 6.4 Conducting Materials 171 6.5 Magnetic Materials 173 6.6 Sensors 177 6.7 Conclusions and Outlook 180 Acknowledgements 181 References 181 7 Chirality in Network Solids 190 David R. Turner 7.1 Introduction 190 7.2 Chirality in Inorganic Network Solids 191 7.3 Synthesis of Chiral Coordination Polymers 192 7.4 Applications of Chiral Coordination Polymers 207 7.5 Summary and Outlook 209 References 210 8 Chiral Metallosupramolecular Polyhedra 218 Jack K. Clegg and John C. McMurtrie 8.1 Introduction 218 8.2 Basic Design Principles 219 8.3 Chiral Polyhedra from Achiral Components 221 8.4 Stereochemical Communication 231 8.5 Resolution of Racemic Metallo?]Supramolecular Polyhedra 236 8.6 Chiral Polyhedra from Chiral Molecular Components 239 8.7 Conclusions and Outlook 250 References 251 9 Chirality at the Solution/Solid?]State Interface 257 Iris Destoop and Steven De Feyter 9.1 Self?]Assembly at the Solution / Solid?]State Interface 257 9.2 Chirality Expression at the Solution / Solid?]State Interface 258 9.3 Chiral Induction / Amplification at the Solution / Solid?]State Interface 266 9.4 Towards Applications 278 9.5 Conclusions 282 References 282 10 Nanoscale Aspects of Chiral Nucleation and Propagation 285 Edward G. Latter and Rasmita Raval 10.1 Introduction 285 10.2 Systems of Discussion 288 10.3 Conclusions 303 References 304 11 Chirality in Organic Hosts 307 Daniel Fankhauser and Christopher J. Easton 11.1 Introduction 307 11.2 Chiral Hosts in Analytical Applications 307 11.3 Chiral Hosts in Asymmetric Reactions 313 11.4 Conclusion 337 Acknowledgements 338 References 338 12 Chirality Related to Biocatalysis and Enzymes in Organic Synthesis 343 Declan P. Gavin and Anita R. Maguire 12.1 Introduction 343 12.2 Biocatalysis 344 12.3 Biocatalytic Methodologies: Kinetic/Dynamic Kinetic Resolution and Asymmetric Transformations/Chemoselective Desymmetrizations 348 12.4 Optimization of Biocatalyst Performance 351 12.5 Protein Engineering 352 12.6 Hydrolysis/Reverse Hydrolysis 356 12.7 Redox Reactions 366 12.8 C?]C and Other C?]X Bond Formation 380 12.9 Future and Outlook 385 References 385 Index 407

About the Author :
Emeritus Professor F. Richard Keene Adjunct Professor of Chemistry, School of Pharmacy & Molecular Sciences, James Cook University, Australia and Department of Chemistry, University of Canterbury, New Zealand. Honorary Visiting Research Fellow, School of Chemistry & Physics, University of Adelaide Richard Keene is an acknowledged international authority on stereochemistry in coordination chemistry - and significantly, in the control of stereochemistry within polymetallic supramolecular assemblies - and has over the last decade has published widely on (i) its effect on intramolecular electron and energy transfer in such assemblies, and (ii) its influence on sequence- and structure-selectivity in the interaction of such complexes with nucleic acids, and their cytotoxicity to cancer cells and bacteria. He has over 160 publications (h-index 44), as well 6 chapters in monographs and a patent.