Solvents as Reagents in Organic Synthesis

Written by highly renowned and experienced authors, this is the only reference on the application of solvents as reagents. Clearly structured, the text describes various methods for the activation and reaction of these small molecules, highlighting the synthetic opportunities as well as process-oriented advantages. To this end, all relevant types of solvents are covered separately and emphasized with numerous synthetic examples, while taking care to explain applications so as to avoid undesired side reactions. The result is a unique resource for every synthetic chemist and reaction engineer in industry and academia working on the methodical optimization of synthetic transformations.

Auteur
180 publications in international journals.

Contenu

List of Contributors xiii

**1 The Applications ofWater as Reagents in Organic Synthesis 1
**Zhengkai Chen and Hongjun Ren

1.1 Introduction 1

1.2 Incorporation of Hydrogen Atom from theWater 2

1.2.1 1,2,3-Triazoles 4

1.3 Incorporation of Oxygen Atom from theWater 7

1.4 Incorporation of Hydroxyl Group fromWater 31

1.5 Traceless Promotion of the Reactions byWater 39

1.6 Conclusions 44

References 44

**2 The Applications of Toluene and Xylenes 49
**Krishna Nand Singh, Narendra R. Chaubey, and Neetu Singh

2.1 Application of Toluene and Xylenes as Reagents 50

2.2 Oxidation of Methyl Group into Common Functionalities 50

2.3 Application of Methyl Group as Acyl Building Block 51

2.3.1 Synthesis of Carbonyl Compounds 51

2.3.2 Synthesis of Amides 53

2.3.3 Synthesis of N-Aroyl Sulfoximines 54

2.3.4 Synthesis of Esters 55

2.3.5 Synthesis of Thioesters 56

2.4 Application as Alkyl Building Block 60

2.4.1 Synthesis of Nitriles 60

2.4.2 Synthesis of 2-Phenyl Acetic Acid Derivatives 61

2.4.3 Alkylation of Sulfonamides 62

2.4.4 Alkylation ofThiophenols 63

2.4.5 Synthesis of Trifluoromethyl Sulfides 64

2.4.6 Synthesis of Benzyl Esters 64

2.4.7 Synthesis of Phosphate Esters 66

2.4.8 Synthesis of Carbamates,Thioamides, and Esters 66

2.4.9 Synthesis of 3-Benzyl Coumarin Derivatives 66

2.4.10 Decarboxylative Benzylation of Cinnamic Acids 68

2.4.11 Synthesis of Functionalized Oxindoles 68

2.4.12 Synthesis of Dihydroquinolinones 69

2.4.13 Benzylation of Enones 69

2.4.14 Coupling with 1,3-Dicarbonyl Compounds 70

2.4.15 Benzylation of Pyridine-N-Oxide 70

2.4.16 Synthesis of Dihydrofurans 70

2.4.17 Synthesis of Quinoline Derivatives 71

2.4.18 Reaction with Ethyl Diazoacetate 72

2.4.19 Synthesis of Benzo[b]phosphole Oxides 72

2.4.20 Synthesis of -Aromatic -Amino Acid Derivatives 73

2.4.21 Halogenation Reactions 73

2.4.22 N-Benzylation of Isoquinolines 75

2.5 Application as Esters Building Block 76

2.6 Application as Alcohols Building Block 77

References 77

**3 The Applications of 1,4-Dioxane, THF, and Ethers as Versatile Building Blocks in Organic Synthesis 81
**Ping Liu, Guanghui Zhang, and Peipei Sun

3.1 Introduction 81

3.2 Cleavage of C(sp3)H of Ethers 82

3.2.1 Cross-Dehydrogenative Coupling Reactions of Ethers 82

3.2.1.1 CC Bond Formation 83

3.2.1.2 CN Bond Formation 91

3.2.1.3 CO Bond Formation 93

3.2.2 The Formation of CS Bond 97

3.2.3 Addition of Ethers to C=C and CC Bonds 98

3.2.4 Decarboxylative Alkenylation or Alkylation Reactions 104

3.2.5 Radical Alkenylation and Alkynylation of Ethers 106

3.2.6 Radical -CH Hydroxyalkylation and Aminoalkylation of Ethers 107

3.2.7 Intermolecular Carbenoid Insertion to -CH Bond of Ethers 109

3.2.8 C(sp3)H Arylation with Arylmetal or Arylboron Reagents 109

3.3 Cleavage of CO of Ethers 112

3.4 Cleavage of CC Bonds of Ethers 117

3.5 Conclusion 118

References 118

**4 The Application of Dichloromethane and Chloroform as Reagents in Organic Synthesis 125
**Anis Tlili and Johannes Schranck

4.1 The Application of Dichloromethane and Chloroform as Reagents in Organic Synthesis 125

4.1.1 Dichloromethane 125

4.1.1.1 Reactions of Dichloromethane with Posttransition Metals 126

4.1.1.2 Reactions of Dichloromethane with Transition Metals 127

4.1.1.3 Reactions of Dichloromethane with Phosphines 135

4.1.1.4 Reactions of Dichloromethane with Amines and Phosphines 136

4.1.1.5 Reactions of Dichloromethane with Amines 136 4.1.1.6 Reactions of Dichloromethane with Amines and Nucleophilic C...