An extensive update of the classic reference on organic reactions
in water

Published almost a decade ago, the first edition has served as the
guide for research in this burgeoning field. Due to the cost,
safety, efficiency, and environmental friendliness of water as a
solvent, there are many new applications in industry and academic
laboratories. More than forty percent of this extensively updated
second edition covers new reactions. For ease of reference, it is
organized by functional groups. A core reference, Comprehensive
Organic Reactions in Aqueous Media, Second Edition:

* Provides the most comprehensive coverage of aqueous
organicreactions available

* Covers the basic principles and theory and progresses to
applications

* Includes alkanes, alkenes, aromatics, electrophilic
substitutions, carbonyls, alpha, beta-unsaturated carbonyls,
carbon-nitrogen bonds, organic halides, pericyclic reactions,
photochemical reactions, click chemistry, and multi-step
syntheses?

* Provides examples of applications in industry

This is the premier reference for chemists and chemical engineers
in industry or research, as well as for students in advanced-level
courses.

Tak-Hang Chan, PhD, is Professor Emeritus at McGill University in Canada and Chair Professor of Organic Chemistry at the Hong Kong Polytechnic University in Hong Kong. In 1993, Professor Chan received the prestigious R.U. Lemieux Award of the Canadian Society of Chemistry. A pioneer in green chemistry, he is a Fellow of the Royal Society of Canada and holds Honorary Professorships at Academia Sinica, Peking University, and Lanzhou University. He was coauthor of the first edition.

Published almost a decade ago, the first edition has served as the guide for research in this burgeoning field. Due to the cost, safety, efficiency, and environmental friendliness of water as a solvent, there are many new applications in industry and academic laboratories. More than forty percent of this extensively updated second edition covers new reactions. For ease of reference, it is organized by functional groups. A core reference, Comprehensive Organic Reactions in Aqueous Media, Second Edition:

• Provides the most comprehensive coverage of aqueous organicreactions available

• Covers the basic principles and theory and progresses to applications

• Includes alkanes, alkenes, aromatics, electrophilic substitutions, carbonyls, alpha, beta-unsaturated carbonyls, carbon-nitrogen bonds, organic halides, pericyclic reactions, photochemical reactions, click chemistry, and multi-step syntheses?

• Provides examples of applications in industry

This is the premier reference for chemists and chemical engineers in industry or research, as well as for students in advanced-level courses.

Preface to the Second Edition xv

1 Introduction 1

1.1 The Structure and Forms of Water 3

1.2 Properties of Water 4

1.3 Solvation 6

1.4 Hydrophobic Effect 6

1.5 Salt Effect 8

1.6 Water Under Extreme Conditions 9

References 13

2 Alkanes 15

2.1 Oxygenation of Alkanes 15

2.2 Halogenation of Alkanes 20

2.3 Formation of CarbonCarbon Bonds 20

2.4 DH Exchange of Alkanes in Water 21

References 22

3 Alkenes 25

3.1 Reduction 25

3.1.1 Hydrogenation 25

3.2 Electrophilic Additions 28

3.2.1 Reaction with Halogen 28

3.2.2 Reaction with Hydrogen Halides 28

3.2.3 Addition of Water 29

3.2.4 OxymercurationOxymetalation 29

3.2.5 Epoxidation 30

3.2.6 Dihydroxylation and Hydroxylamination 35

3.2.7 Wacker's Oxidation 40

3.2.8 Oxidative C=C Bond Cleavage 43

3.2.9 CC Bond Formations 46

3.3 Radical Reactions of Alkenes 47

3.3.1 Radical Polymerization of Alkenes 47

3.3.2 Radical Additions 48

3.3.3 Radical Cyclization 49

3.4 Carbene Reactions 50

3.4.1 The Generation of Carbenes in Aqueous Medium 50

3.4.2 The Stability of Carbenes 50

3.4.3 The Reaction of Carbenes with Alkenes in Aqueous Medium 51

3.5 Alkene Isomerization 52

3.6 Transition-Metal Catalyzed CC Formation Reactions 53

3.6.1 Polymerizations 53

3.6.2 Heck Reactions and Related VinylationArylation 54

3.6.3 Hydrovinylation 56

3.6.4 Reaction with Arenes 56

3.6.5 Hydroformylation 57

3.6.6 Reaction with Alkynes 58

3.6.7 Carbonylation 60

3.6.8 Cycloaddition Reactions of Alkenes 60

3.7 Olefin Metathesis 60

3.7.1 Ring-Opening Metathesis Polymerization (romp) 61

3.7.2 Ring-Closing Metathesis (RCM) 62

3.8 Reaction of Allylic CH Bond 64

3.8.1 Allylic Oxidation 64

3.8.2 CC Bond Formations 65

References 66

4 Alkynes 77

4.1 Reaction of Terminal Alkynes 77

4.1.1 Alkyne Oxidative Dimerization 77

4.1.2 Alkyne-Alkyne Addition 78

4.1.3 Reaction of Alkynes with Organic Halides 81

4.1.4 Reaction of Alkynes with Carbonyl Compounds 93

4.1.5 Reaction of Alkynes with C=N Compounds 94

4.1.6 Conjugate Addition with Terminal Alkynes 97

4.2 Additions of CC bonds 98

4.2.1 Reduction 98

4.2.2 Addition of Water 98

4.2.3 Addition of Alcohols and Amines 100

4.2.4 Hydrosilation and Hydrometalations 102

4.2.5 Addition of Aryls 104

4.2.6 Carbonylation of Internal Alkynes 107

4.2.7 Other Additions to Alkynes 109

4.3 Transition-Metal Catalyzed Cycloadditions 109

4.3.1 Pauson-Khand-Type Reactions 109

4.3.2 [2 + 2 + 2] Cyclotrimerization 111

4.3.3 [2 + 2 + 2] Alkyne-Nitrile Cyclotrimerization 114

4.3.4 [3 + 2] 1,3-Dipolar Cycloaddition 114

4.3.5 [4 + 2] Cycloaddition 118

4.3.6 [5 + 2] Cycloaddition 119

4.3.7 Other Cycloadditions 119

4.4 Other Reactions 121

References 121

5 Alcohols, Phenols, Ethers, Thiols, and Thioethers 129

5.1 Oxidation of Alcohols 129

5.1.1 Diol Cleavage 134

5.2 SubstitutionsElimination 134

5.3 Addition of Alcohols, Phenols, and Thiols to Alkene and Alkyne Bonds 137

5.4 Addition of Alcohols to C=O Bonds: Esterification and Acetal Formations 137

5.5 Reaction of Ethers and Cyclic Ethers 138

5.5.1 Ethers and Cyclic Ethers 138

5.5.2 Reactions of Epoxides in Water and Click Chemistry 139

5.6 Reaction of Sulfur Compounds 141

5.6.1 Oxidation of Thiols and Thioethers 141

5.6.2 Reduction of Disulfides 142