Publisher: Wiley-Blackwell
Number Of Pages: 424
Publication Date: 1991-01-15
ISBN-10 / ASIN: 1405138904
ISBN-13 / EAN: 9781405138901
Binding: Hardcover
Organic Reactions in Water:
Principles, Strategies and Applications
U. Marcus Lindstrom
Contents
Contributors xi
Preface xiii
Foreword xvi
1 A Fifty-Year Perspective on Chemistry in Water 1
RONALD BRESLOW
1.1 Enzyme mimics and models 1
1.1.1 Thiamine 1
1.1.2 Cyclodextrins 2
1.1.3 Cyclodextrins with bound metal ions 4
1.1.4 Cyclodextrin dimers 5
1.1.5 Ribonuclease mimics 6
1.1.6 Transaminase mimics 10
1.1.7 Cytochrome P-450 mimics 14
1.2 Reactions in water promoted by hydrophobic binding of small molecules 15
1.2.1 Diels–Alder reactions 15
1.2.2 The benzoin condensation 17
1.2.3 Atom transfer reactions 18
1.3 Quantitative antihydrophobic effects in water and the geometries of transition states 19
1.4 The importance of water as a reaction solvent 22
2 Structure and Properties of Water 29
JAN B.F.N. ENGBERTS
2.1 Water, the molecule and the liquid 30
2.1.1 The single water molecule 30
2.1.2 Liquid water 32
2.2 Properties of water 35
2.2.1 Solvent properties and parameters 35
2.2.2 Thermodynamics of hydration 41
2.2.3 Hydrophobic interactions 47
2.3 Kinetic solvent effects in aqueous solution 50
3 Acid Catalysis in Water 60
CHIKAKO OGAWA AND SH U KOBAYASHI
3.1 Homogeneous catalysis 60
3.1.1 Brønsted acid catalysis 60
3.1.2 Lewis acid catalysis 62
3.1.3 Asymmetric catalysis 64
3.2 Heterogeneous catalysis 74
3.2.1 Polymer-supported Brønsted catalysis 74
3.2.2 Polymer-supported metal catalysis 77
3.3 Micellar catalysis 79
3.3.1 LASC (Lewis acid-surfactant-combined catalysts) 79
3.3.2 BASC (Brønsted acid-surfactant-combined catalyst) 84
3.4 Conclusion 89
4 Metal-Mediated C C Bond Formations in Aqueous Media 92
CHAO-JUN LI
4.1 Introduction 92
4.2 Reactivity of organometallic compounds with water 93
4.2.1 C M bonding 93
4.2.2 C M hydrolysis 93
4.2.3 C M reactions 94
4.2.4 C C bond formations via C M reactions in water 95
4.3 Allylation of carbonyls and imines 96
4.3.1 Alyllation of carbonyl compounds 97
4.3.2 Allylation of imines and related compounds 113
4.4 Propargylation/allenylation of carbonyls, imines, and related compounds 116
4.5 Metal-mediated benzylation of carbonyls and imines 118
4.6 Arylation and vinylation of carbonyls and imines 118
4.6.1 Arylation and vinylation of aldehydes 119
4.6.2 Arylation and vinylation of imines and related compounds 120
4.7 Alkynylation of carbonyls, imines, and related compounds 121
4.7.1 Alkynylation of aldehydes 121
4.7.2 Alkynylation of imines and related compounds 123
4.7.3 Asymmetric alkynylation 125
4.8 Metal-mediated aldol and Reformatsky-type reactions 125
4.9 Metal-mediated alkylation of carbonyls and imines 127
4.9.1 Alkylation of aldehydes 127
4.9.2 Alkylation of imines 128
4.10 Metal-mediated conjugate addition reactions 129
4.10.1 Addition of alkyl groups 130
4.10.2 Addition of vinyl and aryl groups 131
4.10.3 Addition of alkynes 133
4.11 Metal-mediated coupling reactions 134
4.11.1 Pinacol coupling 134
4.11.2 Other reductive couplings 135
4.11.3 Cross-dehydrogenative coupling 137
4.12 Conclusion 137
5 Pericyclic Reactions in Aqueous Media 146
FRANCESCO FRINGUELLI, ORIANA PIERMATTI, FERDINANDO PIZZO, AND LUIGI VACCARO
5.1 Diels–Alder cycloaddition reactions 146
5.1.1 Carbo Diels–Alder reactions 147
5.1.2 Biocatalyzed carbo Diels–Alder reactions 153
5.1.3 Hetero Diels–Alder reactions 158
5.1.4 The role of water 161
5.2 1,3-Dipolar cycloaddition reactions 163
5.2.1 Pyrrole and pyrrolidine-ring formation 163
5.2.2 Isoxazole and hydroderivative-ring formation 163
5.2.3 Pyrazole and pyrazoline-ring formation 166
5.2.4 Triazole and triazoline-ring formation 167
5.2.5 Tetrazole-ring formation 170
5.3 [2 + 2] Photocycloaddition reactions 171
5.4 Claisen rearrangement reactions 174
6 Catalyzed Reductions in Aqueous Media 185
T.V. RAJANBABU AND SEUNGHOON SHIN
6.1 Special features of catalytic hydrogenation in water by organometallic complexes 186
6.2 Water-soluble complexes for aqueous hydrogenation 187
6.2.1 Sulfonated phosphine and other ligands 187
6.2.2 Nitrogen-containing phosphine ligands 188
6.2.3 Hydroxyphosphine and other oxygen-containing ligands 190
6.3 Hydrogenation of C C bond 194
6.3.1 Reductions of dehydroamino acid and acrylic acid derivatives 194
6.4 Hydrogenation of C O bond 200
6.4.1 Chemoselectivity of C C vs C O bonds 200
6.5 Asymmetric reduction of C O bond in water 201
6.5.1 Asymmetric hydrogenation of C O bond in water 201
6.5.2 Asymmetric transfer hydrogenation of C O bond in water 202
6.5.3 Hydrogenation of C N bond 205
6.6 Miscellaneous reductions: reduction of epoxides, halides, and carbon dioxide 206
6.7 Summary and outlook 206
7 Oxidations 215
ROGER A. SHELDON
7.1 Water-soluble ligands 216
7.2 Oxidations catalyzed by metalloporphyrins and metallophthalocyanines 216
7.3 Epoxidation and dihydroxylation of olefins in aqueous media 218
7.4 Alcohol oxidations in aqueous media 224
7.5 Aldehyde and ketone oxidations in water 231
7.6 Sulfoxidations in water 232
7.7 Concluding remarks 233
8 Nucleophilic Additions and Substitutions in Water 236
DENIS SINOU
8.1 Nucleophilic additions 236
8.1.1 The aldol reaction 236
8.1.2 Michael addition 241
8.1.3 Mannich-type reaction 243
8.2 Nucleophilic substitution 246
8.2.1 Ring-opening nucleophilic substitution 246
8.2.2 Alkylation reactions 248
8.2.3 Other types of substitutions 250
8.3 Conclusion 251
9 Reactions in Nearcritical Water 256
C.L. LIOTTA, J.P. HALLETT, P. POLLET, AND C.A. ECKERT
9.1 Characterization of NCW 257
9.1.1 Physical and thermodynamic properties of NCW 257
9.1.2 Solvatochromic characterization of NCW 263
9.2 Reactions in NCW 269
9.2.1 Hydrolysis of ester and ether 269
9.2.2 Hydrolysis of nitriles 273
9.2.3 Hydration of β-pinene 275
9.2.4 Elimination reactions 276
9.2.5 Friedel–Crafts alkylation reactions 278
9.2.6 Friedel–Crafts acylation reactions 283
9.2.7 Condensation reactions 286
9.2.8 Rearrangements 291
9.2.9 Hydrogen/deuterium exchange 292
9.2.10 General acid/base reactions 294
9.3 Reactions in high-temperature water enriched with CO2 296
9.4 Limitations and safety 296
9.5 Conclusion 297
10 Biocatalysis in Water 301
KAORU NAKAMURA AND TOMOKO MATSUDA
10.1 Basic aspects of biocatalysis 301
10.1.1 Reaction classification 301
10.1.2 Kinetics of enzymatic reactions 301
10.1.3 Reaction mechanism 303
10.1.4 Selectivities 303
10.1.5 Experimental conditions 304
10.2 Reduction 305
10.2.1 Stereochemistry of hydride transfer 305
10.2.2 Baker’s yeast-catalyzed reaction 307
10.2.3 Overexpression of key reductases from baker’s yeast in Escherichia coli 308
10.2.4 Asymmetric reduction by Geotrichum candidum 309
10.2.5 Hydrogen sources 312
10.2.6 Reduction of carbon–carbon double bonds 315
10.2.7 Reduction of hydroperoxides 315
10.2.8 Reduction of sulfoxides 315
10.3 Oxidation 316
10.3.1 Oxidation of alcohols 316
10.3.2 Hydroxylation 318
10.3.3 Baeyer–Villiger oxidations 319
10.3.4 Oxidation of sulfur compounds 319
10.3.5 Oxidative polymerization 319
10.4 Hydrolysis of esters 322
10.4.1 E -value 323
10.4.2 Synthesis of chiral compounds by enzymatic hydrolysis of esters 323
10.4.3 Hydrolysis of sterically hindered esters 323
10.4.4 Hydrolysis of esters with fluorine functionalities 325
10.4.5 Methods of controlling reactivity and enantioselectivity 325
10.4.6 Control of reactivity and enantioselectivity by genetic engineering 326
10.4.7 Hollow-fiber membrane reactor for lipase-catalyzed hydrolysis: synthesis of diltiazem 327
10.4.8 Lipase-catalyzed optical resolution coupled with in situ inversion: synthesis of prallethrin (pyrethroid), etc. 327
10.4.9 Recognition of fluorinated functionalities from unfluorinated group: H vs F 328
10.4.10 P-chiral and S-chiral compounds 330
10.5 Other types of hydrolysis, dehydration and halogenation 330
10.5.1 Hydrolysis of epoxides 331
10.5.2 Hydrolysis of amide and nitrile 331
10.5.3 Dehydration in water for the synthesis of nitriles 331
10.5.4 Desulfonation 331
10.5.5 Direct glycosylation 333
10.5.6 Dehalogenation 335
10.5.7 Fluorination 335
10.6 C C bond formations 337
10.6.1 Aldol reactions 337
10.6.2 Cyanohydrin synthesis 337
10.6.3 Carboxylations 337
10.7 Dynamic kinetic resolution 337
10.7.1 Dynamic kinetic resolution of racemic ketones through asymmetric reduction 339
10.7.2 Dynamic kinetic resolution using hydrolytic enzymes 339
10.7.3 Deracemization 341
10.8 Conclusion 343
11 Chemistry ‘On Water’ – Organic Synthesis in Aqueous Suspension 350
SRIDHAR NARAYAN, VALERY V. FOKIN, AND K. BARRY SHARPLESS
11.1 Background 351
11.2 The unique reactivity of azodicarboxylates on water 357
11.3 Other examples from our work 361
11.4 Applications of the ‘on water’ method 362
11.5 Perspective and conclusion 363
12 Water As a Reaction Solvent – An Industry Perspective 366
ERNST WIEBUS AND BOY CORNILS
12.1 Hydroformylation as the master development 366
12.1.1 General 366
12.1.2 Immobilization with the help of liquid supports 367
12.1.3 Principles 368
12.2 Examples of aqueous-phase catalyses 373
12.2.1 Hydroformylation (RCH/RP process) 373
12.2.2 Other industrially used aqueous biphasic processes 376
12.2.3 Short overview of other (laboratory-scale) reactions 378
12.3 The ‘aqueous’ recycle and recovery of biphasic catalysts 382
12.3.1 Recycle 382
12.3.2 Recovery 385
12.4 Economics of the process 388
12.5 Environmental aspects 389
12.6 Concluding remarks 390
Index of Organic Reactions in Water 398
Index 401
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