Molecular Encapsulation: Organic Reactions in Constrained Systems

Molecular Encapsulation: Organic Reactions in Constrained Systems......Page 5
Contents......Page 7
Preface......Page 15
List of Contributors......Page 19
1.1 Introduction......Page 23
1.2.1 Supramolecular Photoreactions with Crown Ethers......Page 24
1.2.2 Supramolecular Photoreactions with Calixarenes......Page 25
1.2.3 Supramolecular Photoreactions with Cyclodextrins......Page 28
1.2.4 Supramolecular Photoreactions with Cucurbiturils......Page 34
1.3.1 Photochemical Reactions Templated by Deoxyribonucleic Acid (DNA)......Page 37
1.3.2 Photochemical Reactions Mediated by Proteins......Page 40
1.4.1 Photochemical Reactions with Zeolites......Page 43
1.4.2 Photochemical Reactions in Mesoporous Materials......Page 47
1.4.3 Photochemical Reaction with Self-Assembled Molecular Cages......Page 48
1.5.1 Photochemical Reactions with Dendrimers......Page 50
1.5.2 Photochemical Reactions with Hydrogen-Bonding Templates......Page 52
1.5.3 Photochemical Reactions Templated by Cationic Ion......Page 54
1.6 Photoreaction Control by External Variants......Page 56
1.7 Conclusions......Page 58
References......Page 59
2.1 Introduction......Page 65
2.2 Acylations of the Cyclodextrins by Bound Substrates......Page 66
2.3 Catalytic Reactions in Cyclodextrin Cavities: Aromatic Substitution......Page 68
2.4 Other Solvents than Water......Page 69
2.5.1 Catalysed Hydrolysis Reactions......Page 70
2.5.2 Ribonuclease Mimics......Page 71
2.6 Binding by Cyclodextrins and their Dimers and Trimers......Page 75
2.6.1 Transaminase Mimics......Page 76
2.7 Mimics of Enzymes that Use Thiamine Pyrophosphate as a Co-Enzyme......Page 79
2.8 Aldol Condensations Catalysed by Cyclodextrin Derivatives......Page 81
2.10 Mimics of Cytochrome P-450......Page 83
References......Page 87
3.1 Introduction......Page 93
3.2 Regiocontrolled Electrophilic Aromatic Substitutions......Page 95
3.3 Catalysis of Hydrolytic Reactions......Page 97
3.4 A Molecular Reactor for the Synthesis of Indigoid Dyes......Page 99
3.5 Manipulation of Cycloadditions......Page 102
3.6 Conclusion......Page 108
References......Page 109
4.1 Introduction......Page 113
4.2 The Inclusion Phenomena of Cyclodextrins......Page 114
4.3.2 Organic Reactions Mediated by γ-CD......Page 115
4.3.3 Ternary Complex Formation with β-CD......Page 117
4.4.1 Catalytic Systems Based on Metal Complexes......Page 121
4.4.2 Ring Opening Reactions......Page 123
4.4.3 Addition......Page 127
4.4.4 Oxidation and Reduction......Page 130
4.5 Conclusion......Page 132
References......Page 133
5: Reactions in Zeolites......Page 139
5.1 The Confinement Effect......Page 143
5.2 Superelectrophilic Activation in Zeolites......Page 149
5.3 Huisgen [3+2]-Cycloadditions......Page 152
5.4 Multicomponent Reactions......Page 154
5.4.1 H/D Exchange Between Neopentane and Zeolites......Page 156
5.4.3 H/D Exchange and Acidity......Page 157
5.5 Conclusion......Page 159
References......Page 160
6.1 Introduction......Page 167
6.2 Self-Assembled Nanocapsules......Page 168
6.3.1 Encapsulation Effects in Terms of Rate Equation......Page 169
6.3.2 New Reactivities and Selectivities......Page 170
6.3.3 Product Stabilization......Page 171
6.4 Hydrogen Bonded Capsules......Page 172
6.4.1 Stoichiometric 1,3-Dipolar Cycloaddition......Page 173
6.5 Capsules Based on Metal–Ligand Interactions......Page 174
6.6 Tetrahedral Cages Based on Octahedral M3+ Ions......Page 175
6.6.1 Hydrolysis......Page 176
6.6.2 Allylic Alcohol Isomerization......Page 178
6.7 Octahedral and Square Pyramidal Cages Based on Square-Planar M2+ Ions......Page 179
6.7.1 Diels–Alder Reaction......Page 180
6.7.2 Olefin Photodimerization......Page 182
6.8 Hydrophobic Effects as the Driving Force for the Self-Assembly of Nanocapsules......Page 183
6.8.1 Photooxidation......Page 184
6.9 Ligand Template Approach Using Lewis Acid/Base Interactions......Page 186
6.9.1 Hydroformylation......Page 187
6.10 Virus Capsids, Proteins and Micellar Systems......Page 190
6.11 Micellar Systems......Page 191
6.12 Conclusions and Outlook......Page 192
References......Page 193
7.1.1 Supramolecular Chemistry and Enzymes......Page 197
7.1.2 Reagents and Catalysts......Page 199
7.2 Classes of Concave Reagents......Page 202
7.2.1 Strategies for the Construction of Bimacrocycles......Page 203
7.2.2 Ring-closure......Page 204
7.2.3 Concave Acids, Bases and Ligands......Page 207
7.3.1 Reagents......Page 211
7.3.2 Catalysts......Page 212
7.4 Summary and Outlook......Page 215
References......Page 216
8.1 Introduction......Page 223
8.2 Calixarenes as Hosts......Page 224
8.3 Calixarenes as Molecular Platforms......Page 231
8.3.1 Artificial Esterases: Barium(II) Complexes......Page 232
8.3.2 Artificial Esterases: Zinc(II) Complexes......Page 234
8.3.3 Artificial Esterases: Trimetallic Complexes......Page 237
8.3.4 Artificial Nucleases: Zinc(II) Complexes......Page 238
8.3.5 Artificial Nucleases: Copper(II) Complexes......Page 239
8.4 Concluding Remarks......Page 244
References......Page 245
9.1 Introduction......Page 249
9.2 Types of Inner Phase Reactions......Page 252
9.3.1 Amide C−N Bond Rotation and Ring-Flip of Cyclohexanes......Page 253
9.3.2 Spectroscopic Probes......Page 254
9.4.1 Proton Transfer Reactions......Page 255
9.4.2 Electron Transfer Reactions......Page 256
9.4.3 Nucleophilic Substitutions and Isotopic Exchanges......Page 257
9.4.4 Nucleophilic Additions......Page 258
9.5.1 Diazirine Fragmentation......Page 260
9.5.2 Fragmentation of 3-Sulfolene......Page 262
9.6.2 Cyclobutadiene......Page 263
9.6.4 o-Benzyne......Page 265
9.6.5 Phenylcarbene Rearrangement......Page 268
9.6.6 Carbenes......Page 272
9.6.7 Phenylnitrene......Page 273
9.6.8 Norrish Type II Photochemistry......Page 275
9.6.9 Incarcerated Excited States......Page 276
9.6.10 Photoelectron and Triplet Energy Transfer......Page 278
9.6.11 Hemicarcerand-based Photoactive Assemblies......Page 281
Acknowledgements......Page 282
References......Page 283
10.1 Introduction......Page 291
10.2 Encapsulation of Labile Species......Page 292
10.3 Isolation of Non-covalently Bonded Aggregates......Page 297
10.4.1 Viologen Radical Cations......Page 300
10.4.2 Radicals......Page 303
10.4.3 Carbenes......Page 305
10.4.3.1 4-Oxocyclohexa-2,5-dienylidene......Page 307
10.4.3.2 2-Methylcyclohexylidene......Page 308
10.4.3.3 3-Nortricyclanylidene......Page 310
10.4.3.4 Adamantanylidene......Page 311
10.4.3.6 Chloro(phenyl)carbene......Page 314
10.4.3.7 Bicyclo[3.2.1]octan-8-ylidenes......Page 315
10.4.4 Nitrenes......Page 317
10.4.4.2 2-Adamantanyl nitrene......Page 318
10.4.4.3 Ferrocenyl nitrene......Page 319
10.4.4.4 Phenylnitrene......Page 323
References......Page 326
11.1 Introduction......Page 331
11.2 Reversible Dye Encapsulation Inside Organic Container Molecules......Page 333
11.3 Reversible Dye Encapsulation by Biological Receptors......Page 336
11.4 Permanent Dye Encapsulation Inside Rotaxanes......Page 337
11.5 Permanent Encapsulation Inside Inorganic Matrices......Page 342
References......Page 344
12.1 Introduction......Page 349
12.1.1 Hosts......Page 350
12.1.2 Guests......Page 351
12.2.1 Cyclophanes......Page 352
12.2.2 Calix[n]arenes......Page 354
12.2.3 Charged Calixarenes......Page 356
12.2.4 Homooxacalixarenes......Page 361
12.2.5 Resorcinarenes......Page 363
12.3 Extended Hosts and Capsules......Page 365
12.4 Cucurbiturils......Page 370
12.5 Complex Systems and Applications......Page 372
12.5.1 Photoresponsive Hosts......Page 375
12.6 Conclusions......Page 377
References......Page 379
13.1 Introduction......Page 383
13.2 The Biotin–Avidin Technology......Page 385
13.2.2 The Genetic Optimization Dimension......Page 386
13.3 Artificial Hydrogenases......Page 387
13.4 Artificial Allylic Alkylases......Page 389
13.5 Artificial Transfer Hydrogenase......Page 391
13.6 Enantioselective Sulfoxidation Based on Vanadyl-loaded Streptavidin......Page 394
Acknowledgements......Page 395
References......Page 396
14.1 Introduction......Page 399
14.2 Catalysis by Naturally Occurring Ribozymes......Page 400
14.3 How to Generate Artificial RNA and DNA Catalysts......Page 402
14.4 The Catalytic Spectrum of Artificial Ribozymes......Page 405
14.5 Deoxyribozymes – DNA Molecules with Catalytic Properties......Page 408
14.6.1 In Vitro Selection......Page 409
14.6.2 Overall Catalytic Properties......Page 410
14.6.3 Overall Structure of the Ribozyme......Page 411
14.6.4 Architecture of the Catalytic Pocket......Page 412
14.6.5 Interactions Between the Ribozyme and its Substrates and Products......Page 413
14.6.6 Conformational Dynamics and the Roles of Metal Ions......Page 414
14.6.7 Mechanistic Considerations......Page 415
References......Page 416
15.1 Introduction......Page 419
15.2 The Single Micellar Systems: Factors of Concentration and Micellar Microenvironment......Page 420
15.3.2 The Effect of the Clustering of Reverse Micelles on the Reactivity......Page 424
15.4.1 Aqueous Binary System Ionic–Nonionic Surfactants......Page 427
15.4.2 The Binary Surfactant Mixtures in Non-aqueous Media......Page 429
15.5.1 The Conventional Surfactant/Polyethyleneimine Systems......Page 430
15.5.2 The Pyrimidinic Surfactant Based Systems......Page 434
15.5.3 The Calixarene Based Systems......Page 435
15.5.4 The Non-Aqueous Supramolecular Systems......Page 436
15.6 Conclusions......Page 438
References......Page 439
16.1.1 Vesicular Aggregates......Page 443
16.1.2 Solute Encapsulation by Vesicles......Page 448
16.1.3 Binding Locations......Page 449
16.1.4 Experimental Techniques for Measuring Encapsulation Processes......Page 451
16.2 Catalysis by Vesicles. Encapsulation of Reactants......Page 452
16.2.1 Unimolecular Decarboxylation of 6-NBIC......Page 453
16.2.2 The Kemp Elimination: Rate-limiting Proton Transfer......Page 455
16.2.3 Bimolecular Nucleophilic Substitution......Page 456
16.3 Liposomal Encapsulation in Drug Delivery......Page 457
16.3.1 Encapsulated Drugs......Page 458
16.4 Vesicle–Nucleic Acid Interactions: Gene Transfer Using Lipoplexes......Page 460
16.4.1 Lipoplex Formation......Page 461
16.4.2 Lipoplex Structure......Page 462
References......Page 468
17.1 Introduction......Page 477
17.2.1 What are Liposomes (and Fatty Acid Vesicles)......Page 478
17.2.2 Morphology and Methods of Preparation......Page 480
17.2.3 Chemical Compatibility......Page 483
17.3.1 Basic Strategies......Page 484
17.3.2 Theoretical Aspects......Page 488
17.4 A Theoretical Framework for Complex Reactions in Liposomes......Page 492
17.5 Four Cases of Compartmentalized Reactions......Page 495
Acknowledgements......Page 507
Abbreviations......Page 508
References......Page 509
Index......Page 515