Supramolecular Catalysis

Piet W.N.M. van Leeuwen worked at the Koninklijke Shell Laboratorium Amsterdam (1968–1994) heading the homogeneous catalysis group, he is emeritus professor of homogeneous catalysis of the University of Amsterdam (1989–2007) and the Eindhoven University of Technology (2001–2006), the Netherlands, he was Group leader in ICIQ, Tarragona, Spain (2004–2015), and had an IDEX Chair at LPCNO in INSA-Toulouse, France (2015–2020).Matthieu Raynal is a researcher at Sorbonne Université, Paris, France. His current research focuses on the development of supramolecular helical catalysts, the design of functional chiral assemblies, and the structure-property relationship of supramolecular polymers.

• Preface xixSupramolecular Catalysis: An Introduction xxiPart I Ligand–Ligand Interactions 11 Supramolecular Construction of Bidentate Ligands Through Self-assembly by Hydrogen Bonding 3Felix Bauer and Bernhard Breit1.1 Introduction 31.2 Formation of Bidentate Ligands Through Self-assembly via Hydrogen Bonding and Application in Hydroformylation 51.3 Asymmetric Hydrogenation 131.4 Other Catalytic Applications 171.5 Concluding Remarks 21References 222 Self-Assembled Bidentate Ligands in Transition Metal Catalysis; From Fundamental Invention to Commercial Application 27Alexander M. Kluwer, Xavier Caumes, and Joost N. H. Reek2.1 Introduction 272.2 Metal–Ligand Interactions, the SUPRAphos Library 282.3 Supramolecular Bidentate Ligands Based on Hydrogen Bonds, a Toolbox for Evolutionary Catalyst Design 302.4 Formation of Supramolecular Pincer-Type Complexes 342.5 From a Supramolecular Bidentate Ligand to a Catalyst with Substrate Pre-organization 362.6 Outlook 37References 38Part II Self-assembled Nanostructures and Multi-component Assemblies 413 Assembled Ionic Molecular Catalysts and Ligands 43Kohsuke Ohmatsu, Daisuke Uraguchi, and Takashi Ooi3.1 Introduction 433.2 Concept of Ion-Paired Chiral Ligand 443.4 Conclusion 51References 514 Self-amplification of Enantioselectivity in Asymmetric Catalysis by Supramolecular Recognition and Stereodynamics 55Oliver Trapp4.1 Introduction 554.2 Design of an Enantioselective Self-amplifying Catalyst Based on Noncovalent Product–Catalyst Interactions 574.3 The Stereodynamics of the Ligand Core 574.4 Design of Product–Catalyst Adducts and Catalyst Synthesis 594.5 Noncovalent Interaction Studies via NMR Spectroscopy 614.6 Self-amplifying Hydrogenation of 3,5-DNB-ΔAla-OEt 634.7 Concluding Remarks 64Acknowledgments 64References 645 Interlocked Molecules in Enantioselective Catalysis 69Carel Kwamen and Jochen Niemeyer5.1 Introduction 695.2 Rotaxanes in Enantioselective Catalysis 705.3 Catenanes in Enantioselective Catalysis 755.4 Molecular Knots in Enantioselective Catalysis 775.5 Conclusion 78References 786 Catalytic Supramolecular Gels 81Beatriu Escuder6.1 Introduction 816.2 Catalytic LMWGs 826.3 LMWGs in Organocatalysis 826.4 LMWGs in Metallocatalysis 866.5 Multicomponent Supramolecular Materials Involving Catalytic LMWGs 876.6 Concluding Remarks 89Acknowledgments 90References 907 Supramolecular Helical Catalysts 93Laurent Bouteiller and Matthieu Raynal7.1 Introduction 937.2 Concept: Induction of Chirality to Metal Centers Connected to Supramolecular Helices 947.3 Amplification of Chirality in Two-Component Supramolecular Helical Catalysts 977.4 Amplification of Chirality in Three-Component Helical Catalysts 987.5 Switchable Asymmetric Catalysis by Reversible Assembly of Helical Catalysts 1007.6 Dual Stereocontrol of an Asymmetric Reaction by Switchable Helical Catalysts 1017.7 Concluding Remarks 103Acknowledgments 104References 1048 Self-Assembled Multi-Component Supramolecular Catalysts for Asymmetric Reactions 107Guanghui Ouyang, Jian Jiang, and Minghua LiuReferences 114Part III Ligand–Substrate Interactions 1179 Harnessing Ligand–Substrate Non-covalent Interactions for Control of Site-Selectivity in Transition Metal-Catalyzed C–H Activation and Cross-Coupling 119Robert J. Phipps9.1 Introduction 1199.2 C–H Borylation 1209.3 Cross-Coupling 1269.4 Concluding Remarks 128Acknowledgments 129References 12910 Supramolecular Interactions in Distal C–H Activation of (Hetero)arenes 133Jyoti P. Biswas and Debabrata Maiti10.1 Introduction 13310.2 Distal C–H Activation of Arenes 13310.3 Distal C–H Activation of Heterocycles 13710.4 Conclusion 141Acknowledgments 141References 14111 Transition-Metal-Catalyzed, Site- and Enantioselective Oxygen and Nitrogen Transfer Enabled by Lactam Hydrogen Bonds 145Finn Burg and Thorsten Bach11.1 Chiral Lactams as Hydrogen Bonding Sites for Enantioselective Catalysis 14511.2 Enantioselective Addition to Olefins 14711.3 Enantioselective C(sp 3)–H Functionalization 15011.4 Enantioselective Oxidation of Sulfur Centers 15611.5 Concluding Remarks 157Acknowledgments 158References 15812 Supramolecular Substrate Orientation as Strategy to Control Selectivity in Transition Metal Catalysis 161Joost N.H. Reek and Bas de Bruin12.1 Introduction 16112.2 Asymmetric Hydrogenation 16112.3 Substrate Orientation in Hydroformylation Catalysis 16412.4 Substrate Orientation in C—H Borylation 16812.5 Second Coordination Sphere Control in Enantioselective Cobalt-catalyzed Carbene and Nitrene Transfer Reactions 170References 17413 Phosphine Ligands with Acylguanidinium Groups as Substrate-directing Unit 179Felix Bauer and Bernhard Breit13.1 Introduction 17913.2 Hydroformylation of Alkenoic and Alkynoic Acids 17913.3 Aldehyde Reduction and Tandem Hydroformylation–Hydrogenation 18813.4 Concluding Remarks 197References 19814 Chemical Reactions Controlled By Remote Zn···N Interactions Between Substrates and Catalysts 201Jonathan Trouvé and Rafael Gramage-Doria14.1 Introduction 20114.2 Organic Reactions 20214.3 Transition Metal Catalysis 20414.4 Conclusion 207Acknowledgments 207References 207Part IV Catalysis Promoted by Discrete Cages, Capsules, and other Confined Environments 21115 Artificial Enzymes Created Through Molecular Imprinting of Cross-Linked Micelles 213Yan Zhao15.1 Introduction 21315.2 Surface-Cross-Linked Micelles (SCMs) 21315.3 Molecularly Imprinted Nanoparticles (MINPs) via Double Cross-Linking of Micelles 21515.4 MINP-Based Artificial Esterase 21715.5 MINP-Based Artificial Glycosidase 21915.6 MINP-Based Artificial Enzymes for Asymmetric Catalysis and Tandem Catalysis 22315.7 Concluding Remarks 225Acknowledgments 226References 22616 Bioinspired Catalysis Using Innately Polarized Pd 2 L 4 Coordination Cages 229Paul J. Lusby16.1 Introduction 22916.2 A Coordination-Cage Host–Guest Method Based on Polar Interactions 22916.3 From Guest Binding to Catalysis; an Artificial “Diels–Alderase” 23116.4 Base-Free Michael Addition Catalysis 23516.5 Turning Cage-Catalysis Inside Out 23816.6 Concluding Remarks 239Acknowledgments 239References 23917 Supramolecular Catalysis with a Cubic Coordination Cage: Contributions from Cavity and External-Surface Binding 241ChristopherG.P.TaylorandMichaelD.Ward17.1 Introduction: The Host Cage and Its Structure 24117.2 Binding of Organic Guests in the Central Cavity in Water 24217.3 Surface Binding of Anions 24417.4 The Paradigm: Catalysis of the Kemp Elimination 24517.5 Effects of Anion Accumulation Around the Surface: Autocatalysis 24717.6 Catalysis with Noncavity-Bound Guests: Phosphate Ester Hydrolysis and an Aldol Condensation 24917.7 Conclusion 251Acknowledgments 252References 25218 Transition Metal Catalysis in Confined Spaces 255Joost N.H. Reek and Sonja Pullen18.1 Introduction 25518.2 Template Ligand Strategies for Encapsulation of Transition Metal Catalysts 25518.3 Catalyst Encapsulation Strategies for Solar Fuel-Related Reactions 25818.4 Concluding Remarks and Outlook 268References 26819 Catalysis by Metal–Organic Cages: A Computational Perspective 271Giuseppe Sciortino, Gantulga Norjmaa, Jean Didier Maréchal, and Gregori Ujaque19.1 Introduction 27119.2 Looking for a Robust Computational Framework to Study MOCs 27219.3 Applications of Modeling to Confined Catalysis 27419.4 Future Directions 281References 28120 N-heterocyclic Carbene (NHC)-Capped Cyclodextrins for Cavity-Controlled Catalysis 287Sylvain Roland and Matthieu Sollogoub20.1 Introduction: NHC-Capped Cyclodextrin Metal Complexes 28720.2 Orientation of Cyclization Reactions – Five vs. Six-Membered Cycle 28920.3 Control of Regioselectivity 29120.4 Control of Enantioselectivity by the CD Chiral Cavity 29320.5 Substrate Selectivity 29620.6 Protection of Metal Centers and Promotion of Reactive Species 29720.7 Concluding Remarks 299Acknowledgments 299References 29921 Supramolecular Catalysis by Metallohosts Based on Glycoluril 303Jeroen P.J. Bruekers, Johannes A.A.W. Elemans, and Roeland J.M. Nolte21.1 Introduction 30321.2 Rhodium-Based Catalytic Baskets 30421.3 Copper-Based Catalytic Baskets 30621.4 Porphyrin Cage Catalysts 30721.4.1 Epoxidation of Low-Molecular-Weight Alkenes 30721.4.2 Epoxidation of Polymeric Alkenes 31121.4.3 Carbenoid Transfer Reactions with α-Diazoesters 31521.5 Outlook 316Acknowledgments 317References 31722 Catalysis Inside the Hexameric Resorcinarene Capsule: Toward Addressing Current Challenges in Synthetic Organic Chemistry 321Leonidas-Dimitrios Syntrivanis and Konrad Tiefenbacher22.1 Introduction 32122.2 Background 32122.3 Application to Terpene Cyclization 32322.4 Elucidating the Prerequisites for Catalytic Activity Inside the Resorcinarene Capsule 32822.5 Further Applications of Capsule I as Catalyst 32922.6 Concluding Remarks 330Acknowledgments 331References 33123 Supramolecular Organocatalysis Within the Nanospace of Resorcinarene Capsule 335Carmine Gaeta, Carmen Talotta, Margherita De Rosa, Annunziata Soriente, Antonio Rescifina, and Placido Neri23.1 Introduction 33523.2 The Hexameric Resorcinarene Capsule 33723.3 The Hexameric Capsule as H-bonding Organocatalyst 33823.4 The Hexameric Capsule as Brønsted Acid Organocatalyst 33923.5 Iminium Catalysis with a Coencapsulated Cocatalyst 34123.6 Halogen-bond (XB) Catalysis with a Coencapsulated Cocatalyst 34323.7 Concluding Remarks 343Acknowledgment 344References 34424 Resorcin[4]arene Hexamer: From Nanocontainer to Nanocatalyst 347Giorgio Strukul, Fabrizio Fabris, and Alessandro Scarso24.1 Introduction 34724.2 Resorcinarene Capsule as Nanoreactor 34824.3 Resorcin[4]arene Capsule as Nanocatalyst 35224.4 Concluding Remarks 357Acknowledgments 358References 358Part V Supramolecular Organocatalysis and Non-classical Interactions 36125 The Aryl-Pyrrolidine-tert-Leucine Motif as a New Privileged Chiral Scaffold: The Role of Noncovalent Stabilizing Interactions 363Daniel A. Strassfeld and Eric N. Jacobsen25.1 Introduction 36325.2 Foundational Studies 36425.3 Development of the Aryl-Pyrrolidino-tert-Leucine Catalyst Motif 36625.4 Scope of Enantioselective Reactions and Mechanisms Promoted Effectively by Aryl-Pyrrolidine-tert-Leucine HBD Catalysts 36825.5 Mechanisms of Enantioinduction by Aryl-Pyrrolidinetert-Leucino-H-Bond-Donor Catalysts: Case Studies 37425.6 Concluding Remarks 380Acknowledgments 381References 38226 Chiral Triazole Foldamers in Enantioselective Anion-Binding Catalysis 387Alica C. Keuper and Olga García Mancheño26.1 Introduction 38726.2 Triazoles as Anion Receptors 38726.3 Design of Foldamer Triazoles as Hydrogen Bond Donors for Anion-Binding Catalysis 38826.4 Anion-Binding-Catalyzed Enantioselective Reissert-Type Reaction with Silylketene Acetals 38926.5 Reaction with Different Nucleophiles 39126.6 Nucleophilic Dearomatization of Pyrylium Derivatives 39226.7 Folding and Cooperative Multi-Recognition Mechanism 39326.8 Design of Catalytic Transformations Based on Anion-Template Strategies 39426.9 Concluding Remarks 395Acknowledgments 396References 39627 Supramolecular Catalysis via Organic Solids: Templates to Mechanochemistry to Cascades 401Shweta P. Yelgaonkar and Leonard R. MacGillivray27.1 Template Approach for [2+2] Photocycloadditions 40127.2 State of Mechanochemistry 40227.3 Organic Catalysis and Mechanochemistry 40327.4 Cascade Reactions and Mechanochemistry 40727.5 Concluding Remarks 409Acknowledgments 409References 40928 Exploration of Halogen Bonding for the Catalysis of Organic Reactions 413Revannath L. Sutar and Stefan M. Huber28.1 Introduction 41328.2 Halide Abstraction Reactions 41528.3 Activation of Organic Functional Groups 41828.4 Activation of a Metal–Halogen Bond 42128.5 Conclusion 421References 42229 Chalcogen-Bonding Catalysis 427Wei Wang and Yao Wang29.1 Introduction 42729.2 Challenges in Chalcogen-Bonding Catalysis 42829.3 Discovery of Efficient Chalcogen-Bonding Catalysts 42829.4 Chalcogen–Chalcogen Bonding Catalysis 43129.5 Dual Chalcogen–Chalcogen Bonding Catalysis 43329.6 Conclusion Remarks 436Acknowledgments 437References 43730 Asymmetric Supramolecular Organocatalysis: The Fourth Pillar of Catalysis 441Kengadarane Anebouselvy, Kodambahalli S. Shruthi, and Dhevalapally B. Ramachary30.1 Introduction 44130.2 Asymmetric Michael Additions 44230.3 Concluding Remarks 448Acknowledgments 448References 448Part VI Supramolecular Catalysis in Water 45131 Metal Catalysis in Micellar Media 453Giorgio Strukul, Fabrizio Fabris, and Alessandro Scarso31.1 Introduction 45331.2 Oxidation Reactions 45431.3 C—C and C—X Bond Forming Reactions 45731.4 Metal Nanoparticles in Micellar Media 46131.5 Catalyst Surfactant Interactions 463Acknowledgments 465References 46532 Surfactant Assemblies as Nanoreactors for Organic Transformations 467Margery Cortes-Clerget, Joseph R.A. Kincaid, Nnamdi Akporji, and Bruce H. Lipshutz32.1 Introduction 46732.2 Micellar Catalysis: Concepts 46832.3 Ligand Design 47132.4 The “Nano-to-Nano” Effect 47532.5 Reservoir Effect 47632.6 Access to Opportunities for Telescoping Sequences 47832.7 Industrial Applications 48132.8 Conclusions 483References 48433 Compartmentalized Polymers for Catalysis in Aqueous Media 489Fabian Eisenreich and Anja R.A. Palmans33.1 Introduction 48933.2 Folding a Polymer Chain in Water into a Compact Structure 49133.3 Polymer-Supported Ru(II) Catalysis in Water 49533.4 Polymer-Supported Cu(I) and Pd(II) Catalysis in Water 49633.5 Polymer-Supported Organocatalysis in Water 49833.6 Polymer-Supported Photocatalysis in Water 50033.7 Outlook and Conclusions 501Acknowledgments 502References 50234 Phosphines Modified by Cyclodextrins for Supramolecular Catalysis in Water 507Sébastien Tilloy and Eric Monflier34.1 Introduction 50734.2 Synthesis and Properties of CD-Phosphine 1 (CD-P-1) 50834.3 Synthesis and Properties of CD-Phosphine 2 (CD-P-2) 51034.4 Synthesis and Properties of CD-Phosphine 3 (CD-P-3) 51234.5 Synthesis and Properties of CD-Phosphine 4 (CD-P-4) 51334.6 Concluding Remarks 514References 51535 Water-Soluble Yoctoliter Reaction Flasks 519Yahya A. Ismaiel and Bruce C. Gibb35.1 Introduction 51935.2 Deep-Cavity Cavitands 52035.3 The Thermodynamic and Kinetic Features of the Capsular Complexes 52035.4 Assembly State of OA 1 and TEMOA 2 and Guest Packing Motifs Within 52135.5 Photochemistry 52335.6 Thermal Reactions 52835.7 Summary and Conclusions 533Acknowledgments 533References 53336 Chemical Catalyst-Promoted Regioselective Histone Acylation 537Yuki Yamanashi and Motomu Kanai36.1 Introduction 53736.2 Chemical Catalyst-Mediated Synthetic Epigenetics 53736.3 Supramolecular Catalyst Strategy for Protein Modification 53836.4 Supramolecular Catalyst Strategy for Histone Acetylation In Vitro 53836.5 Catalyst-Promoted Selective Acylation Targeting Proteins in Living Cells 54036.6 Chemical Catalyst-Promoted Regioselective Histone Acylation in Living Cells 54336.7 Concluding Remarks 544References 54437 Protein–Substrate Supramolecular Interactions for the Shape-Selective Hydroformylation of Long-Chain α-Olefins 547Peter J. Deuss and Amanda G. Jarvis37.1 Introduction 54737.2 Design of Protein Templates for Shape-Selective ArMs 55137.3 Introduction of a Metal–Ligand Environment into SCP-2L 55237.4 SCP-2L as a Catalytic Scaffold 55337.5 Phosphine Modification of Proteins 55437.6 Application in Biphasic Hydroformylation 55537.7 Structural Studies on the Rhodium Hydroformylases 55737.8 Concluding Remarks 558Acknowledgments 558References 55938 Supramolecular Assembly of DNA- and Protein-Based Artificial Metalloenzymes 561Gerard Roelfes38.1 Introduction 56138.2 DNA-Based Artificial Metalloenzymes 56238.3 Protein-Based Artificial Metalloenzymes 56438.4 Synergistic Catalysis with Artificial Metalloenzymes 56738.5 In Vivo Assembly and Application of LmrR-Based Artificial Metalloenzymes 56838.6 Conclusions 569References 569Part VII Supramolecular Allosteric Catalysts and Replicators 57339 Switchable Catalysis Using Allosteric Effects 575Michael Schmittel39.1 Introduction 57539.2 Allosteric Regulation at Zinc Porphyrin Stations by Catalyst Release 57639.3 Allosteric Regulation of Catalysis at Copper(I) Sites 58039.4 Dynamic Allosteric Regulation of Catalysis 58339.5 The Future: From Allosteric Regulation of Catalysis in a Network to Smart and Autonomous Mixtures 58539.6 Concluding Remarks 586Acknowledgments 586References 58740 Supramolecularly Regulated Enantioselective Catalysts 591Anton Vidal-Ferran40.1 Introduction 59140.2 Seminal Work 59240.3 Supramolecular Regulation of a Preformed Enantioselective Catalyst 59340.4 Supramolecular Regulation of a Prochiral Ligand or Catalyst 59740.5 Concluding Remarks 600Acknowledgments 601References 60141 Emergent Catalysis by Self-Replicating Molecules 605Kai Liu, Jim Ottelé, and Sijbren Otto41.1 Introduction 60541.2 Implementation of Organocatalysis in Self-Replicating Systems 60741.3 The Implementation of Photocatalysis in Self-Replicating Systems 61041.4 Conclusions and Outlook 612References 612Index 615