Preface xix
Supramolecular Catalysis: An Introduction xxi
Part I Ligand-Ligand Interactions 1
1 Supramolecular Construction of Bidentate Ligands Through Self-assembly by Hydrogen Bonding 3
Felix Bauer and Bernhard Breit
1.1 Introduction 3
1.2 Formation of Bidentate Ligands Through Self-assembly via Hydrogen Bonding and Application in Hydroformylation 5
1.3 Asymmetric Hydrogenation 13
1.4 Other Catalytic Applications 17
1.5 Concluding Remarks 21
References 22
2 Self-Assembled Bidentate Ligands in Transition Metal Catalysis; From Fundamental Invention to Commercial Application 27
Alexander M. Kluwer, Xavier Caumes, and Joost N. H. Reek
2.1 Introduction 27
2.2 Metal-Ligand Interactions, the SUPRAphos Library 28
2.3 Supramolecular Bidentate Ligands Based on Hydrogen Bonds, a Toolbox for Evolutionary Catalyst Design 30
2.4 Formation of Supramolecular Pincer-Type Complexes 34
2.5 From a Supramolecular Bidentate Ligand to a Catalyst with Substrate Pre-organization 36
2.6 Outlook 37
References 38
Part II Self-assembled Nanostructures and Multi-component Assemblies 41
3 Assembled Ionic Molecular Catalysts and Ligands 43
Kohsuke Ohmatsu, Daisuke Uraguchi, and Takashi Ooi
3.1 Introduction 43
3.2 Concept of Ion-Paired Chiral Ligand 44
3.4 Conclusion 51
References 51
4 Self-amplification of Enantioselectivity in Asymmetric Catalysis by Supramolecular Recognition and Stereodynamics 55
Oliver Trapp
4.1 Introduction 55
4.2 Design of an Enantioselective Self-amplifying Catalyst Based on Noncovalent Product-Catalyst Interactions 57
4.3 The Stereodynamics of the Ligand Core 57
4.4 Design of Product-Catalyst Adducts and Catalyst Synthesis 59
4.5 Noncovalent Interaction Studies via NMR Spectroscopy 61
4.6 Self-amplifying Hydrogenation of 3,5-DNB-¿Ala-OEt 63
4.7 Concluding Remarks 64
Acknowledgments 64
References 64
5 Interlocked Molecules in Enantioselective Catalysis 69
Carel Kwamen and Jochen Niemeyer
5.1 Introduction 69
5.2 Rotaxanes in Enantioselective Catalysis 70
5.3 Catenanes in Enantioselective Catalysis 75
5.4 Molecular Knots in Enantioselective Catalysis 77
5.5 Conclusion 78
References 78
6 Catalytic Supramolecular Gels 81
Beatriu Escuder
6.1 Introduction 81
6.2 Catalytic LMWGs 82
6.3 LMWGs in Organocatalysis 82
6.4 LMWGs in Metallocatalysis 86
6.5 Multicomponent Supramolecular Materials Involving Catalytic LMWGs 87
6.6 Concluding Remarks 89
Acknowledgments 90
References 90
7 Supramolecular Helical Catalysts 93
Laurent Bouteiller and Matthieu Raynal
7.1 Introduction 93
7.2 Concept: Induction of Chirality to Metal Centers Connected to Supramolecular Helices 94
7.3 Amplification of Chirality in Two-Component Supramolecular Helical Catalysts 97
7.4 Amplification of Chirality in Three-Component Helical Catalysts 98
7.5 Switchable Asymmetric Catalysis by Reversible Assembly of Helical Catalysts 100
7.6 Dual Stereocontrol of an Asymmetric Reaction by Switchable Helical Catalysts 101
7.7 Concluding Remarks 103
Acknowledgments 104
References 104
8 Self-Assembled Multi-Component Supramolecular Catalysts for Asymmetric Reactions 107
Guanghui Ouyang, Jian Jiang, and Minghua Liu
References 114
Part III Ligand-Substrate Interactions 117
9 Harnessing Ligand-Substrate Non-covalent Interactions for Control of Site-Selectivity in Transition Metal-Catalyzed C-H Activation and Cross-Coupling 119
Robert J. Phipps
9.1 Introduction 119
9.2 C-H Borylation 120
9.3 Cross-Coupling 126
9.4 Concluding Remarks 128
Acknowledgments 129
References 129
10 Supramolecular Interactions in Distal C-H Activation of (Hetero)arenes 133
Jyoti P. Biswas and Debabrata Maiti
10.1 Introduction 133
10.2 Distal C-H Activation of Arenes 133
10.3 Distal C-H Activation of Heterocycles 137
10.4 Conclusion 141
Acknowledgments 141
References 141
11 Transition-Metal-Catalyzed, Site- and Enantioselective Oxygen and Nitrogen Transfer Enabled by Lactam Hydrogen Bonds 145
Finn Burg and Thorsten Bach
11.1 Chiral Lactams as Hydrogen Bonding Sites for Enantioselective Catalysis 145
11.2 Enantioselective Addition to Olefins 147
11.3 Enantioselective C(sp 3)-H Functionalization 150
11.4 Enantioselective Oxidation of Sulfur Centers 156
11.5 Concluding Remarks 157
Acknowledgments 158
References 158
12 Supramolecular Substrate Orientation as Strategy to Control Selectivity in Transition Metal Catalysis 161
Joost N.H. Reek and Bas de Bruin
12.1 Introduction 161
12.2 Asymmetric Hydrogenation 161
12.3 Substrate Orientation in Hydroformylation Catalysis 164
12.4 Substrate Orientation in C-H Borylation 168
12.5 Second Coordination Sphere Control in Enantioselective Cobalt-catalyzed Carbene and Nitrene Transfer Reactions 170
References 174
13 Phosphine Ligands with Acylguanidinium Groups as Substrate-directing Unit 179
Felix Bauer and Bernhard Breit
13.1 Introduction 179
13.2 Hydroformylation of Alkenoic and Alkynoic Acids 179
13.3 Aldehyde Reduction and Tandem Hydroformylation-Hydrogenation 188
13.4 Concluding Remarks 197
References 198
14 Chemical Reactions Controlled By Remote Zn···N Interactions Between Substrates and Catalysts 201
Jonathan Trouvé and Rafael Gramage-Doria
14.1 Introduction 201
14.2 Organic Reactions 202
14.3 Transition Metal Catalysis 204
14.4 Conclusion 207
Acknowledgments 207
References 207
Part IV Catalysis Promoted by Discrete Cages, Capsules, and other Confined Environments 211
15 Artificial Enzymes Created Through Molecular Imprinting of Cross-Linked Micelles 213
Yan Zhao
15.1 Introduction 213
15.2 Surface-Cross-Linked Micelles (SCMs) 213
15.3 Molecularly Imprinted Nanoparticles (MINPs) via Double Cross-Linking of Micelles 215
15.4 MINP-Based Artificial Esterase 217
15.5 MINP-Based Artificial Glycosidase 219
15.6 MINP-Based Artificial Enzymes for Asymmetric Catalysis and Tandem Catalysis 223
15.7 Concluding Remarks 225
Acknowledgments 226
References 226
16 Bioinspired Catalysis Using Innately Polarized Pd 2 L 4 Coordination Cages 229
Paul J. Lusby
16.1 Introduction 229
16.2 A Coordination-Cage Host-Guest Method Based on Polar Interactions 229
16.3 From Guest Binding to Catalysis; an Artificial "Diels-Alderase" 231
16.4 Base-Free Michael Addition Catalysis 235
16.5 Turning Cage-Catalysis Inside Out 238
16.6 Concluding Remarks 239
Acknowledgments 239
References 239
17 Supramolecular Catalysis with a Cubic Coordination Cage: Contributions from Cavity and External-Surface Binding 241
ChristopherG.P.TaylorandMichaelD.Ward
17.1 Introduction: The Host Cage and Its Structure 241
17.2 Binding of Organic Guests in the Central Cavity in Water 242
17.3 Surface Binding of Anions 244
17.4 The Paradigm: Catalysis of the Kemp Elimination 245
17.5 Effects of Anion Accumulation Around the Surface: Autocatalysis 247
17.6 Catalysis with Noncavity-Bound Guests: Phosphate Ester Hydrolysis and an Aldol Condensation 249
17.7 Conclusion 251
Acknowledgments 252
References 252
18 Transition Metal Catalysis in Confined Spaces 255
Joost N.H. Reek and Sonja Pullen
18.1 Introduction 255
18.2 Template Ligand Strategies for Encapsulation of Transition Metal Catalysts 255
18.3 Catalyst Encapsulation Strategies for Solar Fuel-Related Reactions 258
18.4 Concluding Remarks and Outlook 268
References 268
19 Catalysis by Metal-Organic Cages: A Computational Perspective 271
Giuseppe Sciortino, Gantulga Norjmaa, Jean Didier Maréchal, and Gregori Ujaque
19.1 Introduction 271
19.2 Looking for a Robust Computational Framework to Study MOCs 272
19.3 Applications of Modeling to Confined Catalysis 274
19.4 Future Directions 281
References 281
20 N-heterocyclic Carbene (NHC)-Capped Cyclodextrins for Cavity-Controlled Catalysis 287
Sylvain Roland and Matthieu Sollogoub
20.1 Introduction: NHC-Capped Cyclodextrin Metal Complexes 287
20.2 Orientation of Cyclization Reactions - Five vs. Six-Membered Cycle 289
20.3 Control of Regioselectivity 291
20.4 Control of Enantioselectivity by the CD Chiral Cavity 293
20.5 Substrate Selectivity 296
20.6 Protection of Metal Centers and Promotion of Reactive Species 297
20.7 Concluding Remarks 299
Acknowledgments 299
References 299
21 Supramolecular Catalysis by Metallohosts Based on Glycoluril 303
Jeroen P.J. Bruekers, Johannes A.A.W. Elemans, and Roeland J.M. Nolte
21.1 Introduction 303
21.2 Rhodium-Based Catalytic Baskets 304
21.3 Copper-Based Catalytic Baskets 306
21.4 Porphyrin Cage Catalysts 307
21.4.1 Epoxidation of Low-Molecular-Weight Alkenes 307
21.4.2 Epoxidation of Polymeric Alkenes 311
21.4.3 Carbenoid Transfer Reactions with ¿-Diazoesters 315
21.5 Outlook 316
Acknowledgments 317
References 317
22 Catalysis Inside the Hexameric Resorcinarene Capsule: Toward Addressing Current Challenges in Synthetic Organic Chemistry 321
Leonidas-Dimitrios Syntrivanis and Konrad Tiefenbacher
22.1 Introduction 321
22.2 Background 321
22.3 Application to Terpene Cyclization 323
22.4 Elucidating the Prerequisites for Catalytic Activity Inside the Resorcinarene Capsule 328
22.5 Further Applications of Capsule I as Catalyst 329
22.6 Concluding Remarks 330
Acknowledgments 331
References 331
23 Supramolecular Organocatalysis Within the Nanospace of Resorcinarene Capsule 335
Carmine Gaeta, Carmen Talotta, Margherita De Rosa, Annunziata Soriente, Antonio Rescifina, and Placido Neri
23.1 Introduction 335
23.2 The Hexameric Resorcinarene Capsule 337
23.3 The Hexameric Capsule as H-bonding Organocatalyst 338
23.4 The Hexameric Capsule as Brønsted Acid Organocatalyst 339
23.5 Iminium Catalysis with a Coencapsulated Cocatalyst 341
23.6 Halogen-bond (XB) Catalysis with a Coencapsulated Cocatalyst 343
23.7 Concluding Remarks 343
Acknowledgment 344
References 344
24 Resorcin[4]arene Hexamer: From Nanocontainer to Nanocatalyst 347
Giorgio Strukul, Fabrizio Fabris, and Alessandro Scarso
24.1 Introduction 347
24.2 Resorcinarene Capsule as Nanoreactor 348
24.3 Resorcin[4]arene Capsule as Nanocatalyst 352
24.4 Concluding Remarks 357
Acknowledgments 358
References 358
Part V Supramolecular Organocatalysis and Non-classical Interactions 361
25 The Aryl-Pyrrolidine-tert-Leucine Motif as a New Privileged Chiral Scaffold: The Role of Noncovalent Stabilizing Interactions 363
Daniel A. Strassfeld and Eric N. Jacobsen
25.1 Introduction 363
25.2 Foundational Studies 364
25.3 Development of the Aryl-Pyrrolidino-tert-Leucine Catalyst Motif 366
25.4 Scope of Enantioselective Reactions and Mechanisms Promoted Effectively by Aryl-Pyrrolidine-tert-Leucine HBD Catalysts 368
25.5 Mechanisms of Enantioinduction by Aryl-Pyrrolidinetert-Leucino-H-Bond-Donor Catalysts: Case Studies 374
25.6 Concluding Remarks 380
Acknowledgments 381
References 382
26 Chiral Triazole Foldamers in Enantioselective Anion-Binding Catalysis 387
Alica C. Keuper and Olga García Mancheño
26.1 Introduction 387
26.2 Triazoles as Anion Receptors 387
26.3 Design of Foldamer Triazoles as Hydrogen Bond Donors for Anion-Binding Catalysis 388
26.4 Anion-Binding-Catalyzed Enantioselective Reissert-Type Reaction with Silylketene Acetals 389
26.5 Reaction with Different Nucleophiles 391
26.6 Nucleophilic Dearomatization of Pyrylium Derivatives 392
26.7 Folding and Cooperative Multi-Recognition Mechanism 393
26.8 Design of Catalytic Transformations Based on Anion-Template Strategies 394
26.9 Concluding Remarks 395
Acknowledgments 396
References 396
27 Supramolecular Catalysis via Organic Solids: Templates to Mechanochemistry to Cascades 401
Shweta P. Yelgaonkar and Leonard R. MacGillivray
27.1 Template Approach for [2+2] Photocycloadditions 401
27.2 State of Mechanochemistry 402
27.3 Organic Catalysis and Mechanochemistry 403
27.4 Cascade Reactions and Mechanochemistry 407
27.5 Concluding Remarks 409
Acknowledgments 409
References 409
28 Exploration of Halogen Bonding for the Catalysis of Organic Reactions 413
Revannath L. Sutar and Stefan M. Huber
28.1 Introduction 413
28.2 Halide Abstraction Reactions 415
28.3 Activation of Organic Functional Groups 418
28.4 Activation of a Metal-Halogen Bond 421
28.5 Conclusion 421
References 422
29 Chalcogen-Bonding Catalysis 427
Wei Wang and Yao Wang
29.1 Introduction 427
29.2 Challenges in Chalcogen-Bonding Catalysis 428
29.3 Discovery of Efficient Chalcogen-Bonding Catalysts 428
29.4 Chalcogen-Chalcogen Bonding Catalysis 431
29.5 Dual Chalcogen-Chalcogen Bonding Catalysis 433
29.6 Conclusion Remarks 436
Acknowledgments 437
References 437
30 Asymmetric Supramolecular Organocatalysis: The Fourth Pillar of Catalysis 441
Kengadarane Anebouselvy, Kodambahalli S. Shruthi, and Dhevalapally B. Ramachary
30.1 Introduction 441
30.2 Asymmetric Michael Additions 442
30.3 Concluding Remarks 448
Acknowledgments 448
References 448
Part VI Supramolecular Catalysis in Water 451
31 Metal Catalysis in Micellar Media 453
Giorgio Strukul, Fabrizio Fabris, and Alessandro Scarso
31.1 Introduction 453
31.2 Oxidation Reactions 454
31.3 C-C and C-X Bond Forming Reactions 457
31.4 Metal Nanoparticles in Micellar Media 461
31.5 Catalyst Surfactant Interactions 463
Acknowledgments 465
References 465
32 Surfactant Assemblies as Nanoreactors for Organic Transformations 467
Margery Cortes-Clerget, Joseph R.A. Kincaid, Nnamdi Akporji, and Bruce H. Lipshutz
32.1 Introduction 467
32.2 Micellar Catalysis: Concepts 468
32.3 Ligand Design 471
32.4 The "Nano-to-Nano" Effect 475
32.5 Reservoir Effect 476
32.6 Access to Opportunities for Telescoping Sequences 478
32.7 Industrial Applications 481
32.8 Conclusions 483
References 484
33 Compartmentalized Polymers for Catalysis in Aqueous Media 489
Fabian Eisenreich and Anja R.A. Palmans
33.1 Introduction 489
33.2 Folding a Polymer Chain in Water into a Compact Structure 491
33.3 Polymer-Supported Ru(II) Catalysis in Water 495
33.4 Polymer-Supported Cu(I) and Pd(II) Catalysis in Water 496
33.5 Polymer-Supported Organocatalysis in Water 498
33.6 Polymer-Supported Photocatalysis in Water 500
33.7 Outlook and Conclusions 501
Acknowledgments 502
References 502
34 Phosphines Modified by Cyclodextrins for Supramolecular Catalysis in Water 507
Sébastien Tilloy and Eric Monflier
34.1 Introduction 507
34.2 Synthesis and Properties of CD-Phosphine 1 (CD-P-1) 508
34.3 Synthesis and Properties of CD-Phosphine 2 (CD-P-2) 510
34.4 Synthesis and Properties of CD-Phosphine 3 (CD-P-3) 512
34.5 Synthesis and Properties of CD-Phosphine 4 (CD-P-4) 513
34.6 Concluding Remarks 514
References 515
35 Water-Soluble Yoctoliter Reaction Flasks 519
Yahya A. Ismaiel and Bruce C. Gibb
35.1 Introduction 519
35.2 Deep-Cavity Cavitands 520
35.3 The Thermodynamic and Kinetic Features of the Capsular Complexes 520
35.4 Assembly State of OA 1 and TEMOA 2 and Guest Packing Motifs Within 521
35.5 Photochemistry 523
35.6 Thermal Reactions 528
35.7 Summary and Conclusions 533
Acknowledgments 533
References 533
36 Chemical Catalyst-Promoted Regioselective Histone Acylation 537
Yuki Yamanashi and Motomu Kanai
36.1 Introduction 537
36.2 Chemical Catalyst-Mediated Synthetic Epigenetics 537
36.3 Supramolecular Catalyst Strategy for Protein Modification 538
36.4 Supramolecular Catalyst Strategy for Histone Acetylation In Vitro 538
36.5 Catalyst-Promoted Selective Acylation Targeting Proteins in Living Cells 540
36.6 Chemical Catalyst-Promoted Regioselective Histone Acylation in Living Cells 543
36.7 Concluding Remarks 544
References 544
37 Protein-Substrate Supramolecular Interactions for the Shape-Selective Hydroformylation of Long-Chain ¿-Olefins 547
Peter J. Deuss and Amanda G. Jarvis
37.1 Introduction 547
37.2 Design of Protein Templates for Shape-Selective ArMs 551
37.3 Introduction of a Metal-Ligand Environment into SCP-2L 552
37.4 SCP-2L as a Catalytic Scaffold 553
37.5 Phosphine Modification of Proteins 554
37.6 Application in Biphasic Hydroformylation 555
37.7 Structural Studies on the Rhodium Hydroformylases 557
37.8 Concluding Remarks 558
Acknowledgments 558
References 559
38 Supramolecular Assembly of DNA- and Protein-Based Artificial Metalloenzymes 561
Gerard Roelfes
38.1 Introduction 561
38.2 DNA-Based Artificial Metalloenzymes 562
38.3 Protein-Based Artificial Metalloenzymes 564
38.4 Synergistic Catalysis with Artificial Metalloenzymes 567
38.5 In Vivo Assembly and Application of LmrR-Based Artificial Metalloenzymes 568
38.6 Conclusions 569
References 569
Part VII Supramolecular Allosteric Catalysts and Replicators 573
39 Switchable Catalysis Using Allosteric Effects 575
Michael Schmittel
39.1 Introduction 575
39.2 Allosteric Regulation at Zinc Porphyrin Stations by Catalyst Release 576
39.3 Allosteric Regulation of Catalysis at Copper(I) Sites 580
39.4 Dynamic Allosteric Regulation of Catalysis 583
39.5 The Future: From Allosteric Regulation of Catalysis in a Network to Smart and Autonomous Mixtures 585
39.6 Concluding Remarks 586
Acknowledgments 586
References 587
40 Supramolecularly Regulated Enantioselective Catalysts 591
Anton Vidal-Ferran
40.1 Introduction 591
40.2 Seminal Work 592
40.3 Supramolecular Regulation of a Preformed Enantioselective Catalyst 593
40.4 Supramolecular Regulation of a Prochiral Ligand or Catalyst 597
40.5 Concluding Remarks 600
Acknowledgments 601
References 601
41 Emergent Catalysis by Self-Replicating Molecules 605
Kai Liu, Jim Ottelé, and Sijbren Otto
41.1 Introduction 605
41.2 Implementation of Organocatalysis in Self-Replicating Systems 607
41.3 The Implementation of Photocatalysis in Self-Replicating Systems 610
41.4 Conclusions and Outlook 612
References 612
Index 615
