Handbook of Green Chemistry, Volume 5: Reactions in Water

This is the second set of three volumes within the 12-volume Handbook of Green ChemistryThese volumes cover Supercritical Solvents, Reactions in Water and Ionic LiquidsProvides a comprehensive overview of current state-of-the-art-research for the growing field of green chemistry and engineeringCovers topics like feedstocks, green chemistry engineering, green catalysis (homogeneous, heterogeneous and biocatalysis), separations techniques, solvents like supercritical fluids and ionic liquids, this handbook will be without a doubt the one-stop reference book 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 In a world where the emphasis has shifted to being as Green and environmentally friendly as possible, leads to the requirement of this important 3-book set of the Handbook of Green Chemistry edited by the father and pioneer of Green Chemistry, Professor Paul Anastas. This series summarises the significant body of work that has accumulated over the past decade that details the breakthroughs, innovation and creativity within Green Chemistry and Engineering. Set II comprises of 3 books, with each volume focussing on a different area and edited by leading scientists in the Supercritical Solvents - W. Leitner and P. G. Jessop Ionic Liquids - P. Wasserscheid and A. Stark Reactions in Water - C.-J. Li An essential collection for anyone wishing to gain an understanding of the world of green chemistry and for a variety of chemists, environmental agencies and chemical engineers.