Handbook of Green Chemistry, Volume 5: Reactions in Water

Handbook of Green Chemistry, Volume 5: Reactions in Water......Page 1
Contents......Page 2
1.1 Introduction......Page 3
1.2 Binding of Two Species Together Driven by the Hydrophobic Effect in Water......Page 4
1.3 Aromatic Chlorination......Page 5
1.4 Acylation of Cyclodextrins by a Bound Ester......Page 6
1.5 Mimics of Metalloenzymes Using the Hydrophobic Effect in Water......Page 7
1.6 Mimics of the Enzyme Ribonuclease......Page 9
1.7 Mimics of Enzymes that Use Pyridoxamine Phosphate and Pyridoxal Phosphate as Coenzymes......Page 11
1.8 Artificial Enzymes Carrying Mimics of Thiamine Pyrophosphate......Page 17
1.9 Enolizations and Aldol Condensations......Page 19
1.11 Selectivities in Water Induced by the Hydrophobic Effect – Carbonyl Reductions......Page 20
1.12 Selectivities in Water Induced by the Hydrophobic Effect – Oxidations......Page 21
1.13 Using Hydrophobic Effects in Water to Determine the Geometries of Transition States for Some Important Reactions......Page 23
References......Page 27
Introduction. Lewis Acids in Aqueous Media: Possible?......Page 33
Lewis Acid Catalysis in Water as "Sole Solvent"......Page 34
LASC: Lewis Acid–Surfactant Combined Catalyst......Page 35
Polymer-supported Scandium Triflate......Page 36
Silica Gel-supported Scandium with Ionic Liquid......Page 37
Mannich-type Reactions in Water......Page 38
Michael Reaction in Water......Page 39
Epoxide Ring-opening Reaction in Water......Page 41
Hydroxymethylation in Water......Page 42
Surfactant-type Brønsted Acid Catalysts......Page 47
Polymer-supported Brønsted Acid Catalysts......Page 52
References......Page 55
3.1 Introduction......Page 59
3.2 Types of Bases and Their Use from a Green Point of View......Page 60
3.3 Liquid–Liquid Processes......Page 61
3.4 Solid–Liquid Processes......Page 67
References......Page 72
4.1 Introduction......Page 77
4.3 Oxidations Catalyzed by Metalloporphyrins and Metallophthalocyanines......Page 78
4.4 Epoxidation and Dihydroxylation of Olefins in Aqueous Media......Page 80
4.5 Alcohol Oxidations in Aqueous Media......Page 87
4.6 Aldehyde and Ketone Oxidations in Water......Page 96
4.7 Sulfoxidations in Water......Page 98
4.8 Conclusion......Page 99
References......Page 100
5.1 Introduction......Page 107
5.2 Water-soluble Ligands......Page 108
Water-soluble Achiral Ligands......Page 109
5.3 Hydrogenation in Water......Page 110
Hydrogenation of Olefins......Page 111
Hydrogenation of Carbonyl Compounds......Page 115
Hydrogenation of Aromatic Rings......Page 116
Hydrogenation of Other Organic Groups......Page 117
Hydrogenation of CO2......Page 118
Asymmetric Hydrogenation of Olefins......Page 120
Asymmetric Hydrogenation of Carbonyl and Related Compounds......Page 123
5.4 Transfer Hydrogenation in Water......Page 125
Achiral Transfer Hydrogenation of Carbonyl Compounds......Page 126
Asymmetric Transfer Hydrogenation of Ketones......Page 128
Asymmetric Transfer Hydrogenation of Imines......Page 134
Asymmetric Transfer Hydrogenation with Biomimetic Catalysts......Page 135
Water-facilitated Catalyst Separation and Recycle......Page 137
5.5 Role of Water......Page 139
Coordination to Metals......Page 140
Acid–Base Equilibrium......Page 141
H–D Exchange......Page 142
Participation in Transition States......Page 143
References......Page 144
Grignard-type Reactions......Page 153
Allylation Reaction......Page 154
Propargylation and Allenylation Reaction......Page 158
Alkylation Reaction......Page 159
Arylation and Vinylation Reactions......Page 160
Alkynylation Reaction......Page 163
Pinacol Coupling......Page 164
Hydroformylation Reaction......Page 165
Hydroxycarbonylation......Page 166
Isomerization of Alkenes......Page 167
Mizoroki–Heck Reaction and Related Hydroarylation Reactions......Page 168
Cyclization and Cyclotrimerization of Polyfunctional Unsaturated Derivatives......Page 169
Telomerization of Dienes......Page 172
1,4-Addition to a,b-Unsaturated Derivatives......Page 173
Homo- and Heterocoupling Reactions......Page 174
Palladium-catalyzed Reactions (Aryl and Vinyl Iodides, Triflates, Bromides, and Diazoniums salts)......Page 175
Stille Reaction......Page 182
Sonogashira Reaction, Alkyne Oxidative Dimerization......Page 183
Tsuji–Trost Reaction......Page 188
Hiyama Reaction......Page 191
References......Page 193
7.1 Introduction......Page 209
7.2 Pericyclic Reactions......Page 210
7.3 Addition of Heteronucleophiles to Unsaturated Carbonyl Compounds......Page 213
7.4 Enantioselective Direct Aldol Reactions......Page 215
Transition Metal-catalyzed Cross-coupling Reactions......Page 217
Dehydrogenative Coupling Reactions......Page 218
7.6 Oxidation......Page 223
7.7 Bromination Reactions......Page 225
Nucleophilic Substitution......Page 226
Functionalization of SWNTs......Page 227
7.9 Theoretical Studies......Page 228
References......Page 229
Pericyclic Reactions......Page 231
Water, the Ultimate Green Solvent......Page 234
Normal and Inverse Electron-demand Diels–Alder Reactions in Water......Page 236
Intramolecular Diels–Alder Reactions......Page 244
Retro-Diels–Alder Reactions......Page 245
Forward and Retro-hetero-Diels–Alder Reactions......Page 246
Photocycloadditions......Page 250
1,3-Dipolar Cycloadditions......Page 251
Claisen Rearrangements......Page 253
Mixed Aqueous Binary Mixtures......Page 254
"On Water" Pericyclic Reactions......Page 256
(Bio)catalysis, Cyclodextrins, Surfactant Aggregates, Molecular Cages, Microwaves, Supercritical Water......Page 257
(Bio)catalysis......Page 258
Catalysis by Cyclodextrins......Page 261
Catalysis by Surfactant Aggregates......Page 263
Microwave-assisted Aqueous Pericyclic Reactions......Page 268
8.3 Conclusion......Page 269
References......Page 270
9.1 Introduction......Page 275
Carbon–Carbon Coupling Reactions......Page 276
Nitrogen-containing Heterocycles......Page 279
Oxygen-containing Heterocycles......Page 282
Other Miscellaneous Reactions......Page 284
Synthesis of Heterocycles......Page 287
Pinacol Coupling Reaction......Page 288
9.4 Photochemical Transformations in Aqueous Media......Page 289
References......Page 290
10.1 Introduction......Page 293
Knoevenagel Condensations......Page 294
Barbier-type Reactions......Page 299
Baylis–Hillman Reactions......Page 307
Electrophilic Aromatic Substitution Reactions......Page 308
Mukaiyama Aldol Reaction......Page 310
Glycosylamines and Glycamines......Page 311
Aza Sugars......Page 313
10.4 Functionalization of Hydroxy Groups......Page 314
Esterification, Etherification, Carbamation: the Example of Sucrose......Page 315
Oxidation Reactions......Page 320
10.5 Glyco-organic Substrates and Reactions in Aqueous Sugar Solutions......Page 321
References......Page 326
11.1 Introduction......Page 333
Properties of HTW......Page 334
Process Engineering Considerations......Page 336
Theoretical, Computational, and Experimental Methods......Page 337
Classical Theory......Page 338
Molecular and Computational Modeling......Page 339
Experimental Methods......Page 340
pH Effects......Page 341
Hydrogenation......Page 345
Friedel–Crafts Alkylation......Page 346
Heck Coupling......Page 347
Condensation......Page 348
Hydrolysis......Page 350
Rearrangements......Page 352
Hydration/Dehydration......Page 353
Elimination......Page 355
Partial Oxidation to Form Carboxylic Acids......Page 356
Amidation......Page 357
References......Page 358
12.2 Water-based Enzymatic Processes......Page 365
The Pregabalin (Lyrica) Process......Page 366
The Enzymatic Process to Make Rosuvastatin (Crestor) Intermediate 5......Page 368
Enzymatic Routes to Atorvastatin (Lipitor)......Page 369
The Enzymatic Process to Make LY300164......Page 371
The Enzymatic Process to Prepare 6-Aminopenicillanic Acid......Page 373
Enzymatic Routes to Oseltamivir Phosphate (Tamiflu)......Page 374
The Sampatrilat Process......Page 376
12.4 Carbon–Carbon Bond-forming Cross-coupling Reactions in Water......Page 377
Process to Make Compound 29 an Intermediate for a Drug Candidate to Treat Depression......Page 378
An Aqueous Suzuki Reaction to Prepare Diflusinal 33......Page 379
12.5 Pharmaceutical Processes Using Mixed Aqueous Solvents......Page 380
An Environmentally Friendly Baylis–Hillman Process......Page 381
12.6 Conclusion......Page 382
References......Page 384
13.1 Introduction......Page 387
General Aspects of Hydroformylation......Page 388
Cobalt-based Hydroformylation Catalysts and Processes......Page 390
Rhodium-based Hydroformylation Catalysts and Processes......Page 391
Ligands Used for Catalyst Modification......Page 393
Central Questions in Hydroformylation Processes......Page 394
Aqueous–Organic Biphasic Catalysis......Page 395
Aqueous–Organic Biphasic Hydroformylation......Page 396
The Ruhrchemie–Rhône-Poulenc Process......Page 397
Green Features of the Ruhrchemie–Rhône-Poulenc Process......Page 400
Hydroformylation of Longer Chain Alkenes in Aqueous–Organic
Biphasic Systems......Page 401
Developments in Reactor Design for Aqueous–Organic Biphasic
Hydroformylations......Page 402
Catalyst Recovery by Water-induced Phase Separation......Page 403
13.4 Water as Solvent in the Production of 2,7-Octadien–1-ol (Kuraray Process)......Page 405
13.5 Conclusion......Page 407
References......Page 408