Oxidation of C-H bonds / Wenjun Lu and Lihong Zhou.

Format:

Book

Author/Creator:

Lu, Wenjun, 1966- author.

Zhou, Lihong, 1985- author.

Language:

English

Subjects (All):

Organometallic compounds--Oxidation.

Organometallic compounds.

Oxidation.

Organometallic chemistry.

Carbon compounds.

Hydrogen bonding.

Physical Description:

xii, 508 pages ; 25 cm

Place of Publication:

Hoboken, NJ : John Wiley & Sons, Inc., 2017.

Summary:

Oxidation reactions are extremely important and belong to the most employed reactions in the chemical industry. Many reaction pathways (mechanisms), different reaction conditions, and corresponding oxidation reagents have bee realized and established to make the oxidation of C-H bonds more efficient and practical in organic synthesis. Oxidation of C-H Bonds combines oxidation methods and C-H bond functionalization, two of the most important aspects of organic synthesis, in a unique guide for practicing chemists. Coverage includes early reactions, development, and updated examples of the functionalization of various C-H bonds. Since many fundamental concepts about reactions, mechanisms, and synthesis strategies will be explained and discussed in the text, it is also very beneficial to chemistry students and those in need of a primer. Featuring the perspectives and expertise of practicing chemical researchers, this book provides a valuable reference and resource for the organic chemist community. Key benefits include: Offers a guide or manual to solve challenges of chemical transformation, Deals with C-H bonds, an area of dynamic and continuous research across chemistry and catalysis, Helps readers understand the fundamental and applied differences among various oxidation methods and reactions, Emphasizes mechanistic understanding of reactions and critical analysis of them Book jacket.

Contents:

1 Introduction 1

1.1 What Is Oxidation of C-H Bonds? 1

1.2 Chemical Synthesis and Oxidation of C-H Bonds 2

1.2.1 Transformation of Organic Compounds 2

1.2.2 Ideal Chemical Synthesis 2

1.2.3 Oxidation of C-H Bonds for Ideal Chemical Synthesis 3

1.3 C-H Bonds 6

1.3.1 Reactivity 7

1.3.2 Cleavage of Inert C-H Bonds 10

1.3.2.1 Direct Cleavage 10

1.3.2.2 Indirect Cleavage of Inert sp²C-H Bonds 12

1.3.3 Oxidation 13

1.3.3.1 Redox Processes 13

1.3.3.2 Oxidative Processes 14

1.4 Concepts in This Book 15

References 17

2 Oxidation of Methane 19

2.1 Methane 19

2.2 Methyl sp³C-H Bond 20

2.3 Oxidations of Methyl sp³C-H Bond 21

2.3.1 Syngas (CO/H₂) 21

2.3.2 Methanol 23

2.3.3 Ethylene 27

2.3.4 Benzene 29

2.3.5 Acetic Acid 30

2.3.6 Methyl Halide 33

2.4 Summary 35

References 36

3 Oxidation of Alkyl sp³C-H Bond 39

3.1 Alkane 39

3.2 Alkyl sp³C-H Bonds 40

3.3 Oxidations of Alkyl sp³C-H Bond 42

3.3.1 C-C Bond Formation 42

3.3.1.1 Alkenes and Arenes (Dehydrogenation) 43

3.3.1.2 Aliphatic Carboxylic Acids (Carboxylation) and Vinyl Alkanes (Alkenylation) 45

3.3.1.3 Alkylation (Metal-Carbene-Induced C-H Insertion) 48

3.3.2 C-N Bond Formation 51

3.3.2.1 Alkylamines (Amination) 51

3.3.2.2 Nitroalkanes (Nitration) 53

3.3.3 C-O Bond Formation 55

3.3.3.1 Alcohols (Hydroxylation) 55

3.3.4 C-Halogen Bond Formation 57

3.3.4.1 C-F Bond (Fluorination) 57

3.3.4.2 C-CI Bond and C-Br Bond (Chlorination and Bromination) 59

3.3.4.3 G-I Bond (Iodination) 60

3.4 Summary 61

References 62

4 Oxidation of Alkyl sp³C-H Bond Assisted by Directing Group 65

4.1 Directing Group 65

4.2 Alkyl sp³C-H Bonds with Directing Groups 66

4.3 Directed Oxidations of Alkyl sp³C-H Bond 67

4.3.1 C-C Bond Formation 68

4.3.1.1 Alkylation 68

4.3.1.2 Alkenylation 70

4.3.1.3 Alkynylation 73

4.3.1.4 Carbonylation 74

4.3.1.5 Arylation 76

4.3.2 C-N Bond Formation 82

4.3.2.1 Intramolecular Coupling 82

4.3.2.2 Inter molecular Coupling 87

4.3.3 C-O Bond Formation 90

4.3.4 C-Halogen Bond Formation 93

4.4 Summary 97

References 97

5 Oxidation of Alkyl sp³C-H Bond Adjacent to Unsaturated Carbon Atom 101

5.1 Alkyl α-sp³C-H Bond 101

5.2 Alkyl sp³C-H Bonds Adjacent to Unsaturated Carbon Atoms 102

5.3 Oxidations of Alkyl sp³C-H Bond Adjacent to Unsaturated Carbon Atom 103

5.3.1 C-C Bond Formation 103

5.3.1.1 Alkylation 103

5.3.1.2 Arylation 109

5.3.2 C-N Bond Formation 115

5.3.2.1 Amination of Allylic and Benzylic sp³C-H Bonds 115

5.3.2.2 Amination of Active sp³C-H Bonds 118

5.3.3 C-O Bond Formation 120

5.3.4 C-Halogen Bond Formation 129

5.3.4.1 Chlorination and Bromination 129

5.3.4.2 Fluorinating Reagent and Enanttioselective Fluorination 131

5.4 Summary 138

References 138

6 Oxidation of Alkyl sp³C-H Bond Adjacent to Heteroatom 143

6.1 Alkyl sp³C-H Bonds Adjacent to Heteroatoms 143

6.2 Oxidations of Alkyl sp3C-H Bond Adjacent to Heteroatom 144

6.2.1 C-C Bond Formation 145

6.2.1.1 Electrophilic Attack 145

6.2.1.2 Nucleophilic Attack 149

6.2.2 C-N Bond Formation 157

6.2.2.1 Nitrene Reagents 157

6.2.2.2 Other Nucleophiles as Nitrogen Sources 159

6.2.3 C-O Bond Formation 161

6.2.4 Others 166

6.3 Summary 166

References 167

7 Oxidation of Alkenyl or Carbonyl sp²C-H Bond 171

7.1 Alkenyl and Carbonyl sp²C-H Bonds 171

7.2 Oxidations of Alkenyl and Carbonyl sp²C-H Bonds 172

7.2.1 C-C Bond Formation 173

7.2.1.1 Arylation and Alkenylation of Alkenes (The Mizoroki-Heck Coupling Reaction) 173

7.2.1.2 Alkylation of Alkenes 183

7.2.1.3 Alkylation and Alkenylation of sp²C-H Bonds on Aldehydes (Hydroacylation and Coupling Reaction) 184

7.2.1.4 Alkynylation of sp²C-H Bonds on Aldehydes 192

7.2.1.5 Arylation of sp²C-H Bonds on Aldehydes 193

7.2.2 C-Heteroatom Bond Formation 195

7.2.2.1 Oxygenation and Amination of Alkenyl sp²C-H Bonds (The Wacker and Aza-Wacker Processes) 196

7.2.2.2 Esterification and Amidation of Carbonyl sp²C-H Bonds 200

7.3 Summary 203

References 204

8 Oxidation of Alkynyl spC-H Bond 209

8.1 spC-H Bonds 209

8.2 Oxidations of spC-H Bond 210

8.2.1 Oxidations of Alkynyl spC-H Bond 210

8.2.1.1 Nucleophilic Substitution (Formation of spC-sp³C and spC-sp²C Bonds) 210

8.2.1.2 The Sonogashira Reaction (Formation of spC-sp²C and spC-sp³C Bonds) 211

8.2.1.3 Carbonylation and Carboxylation (Formation of spC-sp²C Bonds) 218

8.2.1.4 Glaser-Eglinton-Hay Homocoupling and Cadiot-Chodkiewicz Cross-Coupling (Formation of spC-spC Bonds) 226

8.2.1.5 Formation of Alkynyl spC-Heteroatom Bonds 228

8.2.2 Oxidations of spC-H Bond of Hydrogen Cyanide 231

8.3 Summary 232

References 232

9 Oxidation of Benzene 235

9.1 Introduction 235

9.2 Oxidations of Phenyl sp²C-H Bond 237

9.2.1 Formation of C-C Bond 238

9.2.1.1 Alkylation 238

9.2.1.2 Trifluoromethylation 243

9.2.1.3 Arylation 246

9.2.1.4 Alkenylation 252

9.2.1.5 Carbonylation and Carboxylation 259

9.2.2 Formation of C-N Bond 263

9.2.3 Formation of C-O Bond 265

9.2.4 Formation of C-Halogen Bond 273

9.2.4.1 Fluorination 273

9.2.4.2 Chlorination 275

9.2.4.3 Bromination 276

9.2.4.4 Iodination 276

9.3 Summary 277

References 279

10 Oxidation of Aryl sp²C-H Bond on Substituted Benzene 283

10.1 Introduction 283

10.2 Formation of C-C Bond 284

10.2.1 Alkylation 284

10.2.2 Trifluoromethylation 290

10.2.3 Arylation 294

10.2.4 Alkenylation 298

10.2.5 Acylation and Carboxylation 305

10.2.6 Alkynylation 310

10.2.7 Cyanidation 312

10.3 Formation of C-N Bond 313

10.4 Formation of C-O Bond 316

10.5 Formation of C-S Bond 322

10.6 Formation of C-Halogen Bond 323

10.6.1 Fluorination 323

10.6.2 Chlorination 324

10.6.3 Bromination 327

10.6.4 Iodination 330

10.7 Summary 331

References 333

11 Oxidation of Aryl sp²C-N Bond Assisted by Directing Group 337

11.1 Introduction 337

11.2 Formation of C-C Bond 337

11.2.1 Alkylation 337

11.2.2 Trifluoromethylation 348

11.2.3 Arylation 351

11.2.4 Alkenylation 369

11.2.5 Carbonylation and Carboxylation 390

11.2.6 Alkynylation 393

11.2.7 Cyanidation 399

11.3 Formation of C-N Bond 400

11.4 Formation of C-O Bond 406

11.5 Formation of C-S Bond 412

11.6 Formation of C-Halogen Bond 414

11.6.1 Fluorination 414

11.6.2 Chlorination 416

11.6.3 Bromination 419

11.6.4 Iodination 422

11.7 Summary 424

References 426

12 Oxidation of Aryl sp²C-H Bond on Heteroarene or Perfluoroarene 433

12.1 Introduction 433

12.2 Formation of C-C Bond 434

12.2.1 Alkylation 434

12.2.2 Trifluoromethylation 439

12.2.3 Arylation 441

12.2.4 Alkenylation 449

12.2.5 Carbonylation and Carboxylation 454

12.2.6 Alkynylation 456

12.2.7 Cyanidation 458

12.3 Formation of C-N Bond 459

12.4 Formation of C-O Bond 461

12.5 Formation of C-Halogen Bond 462

12.5.1 Fluoridation 462

12.5.2 Chlorination 464

12.5.3 Bromination 465

12.5.4 Iodination 467

12.6 Cross-Coupling of Dual Aryl sp²C-H Bonds on Directing-Group-Containing Arenes, Heteroarenes, or Polyfluoroarenes 468

12.7 Summary 477

References 478

13 Oxidative Cross-Coupling of Aryl sp²C-H Bond with inert C-H Bond 483

13.1 Introduction 483

13.2 Oxidative Coupling of Simple Arenes with Alkanes (Alkylation of Arenes) 484

13.3 Oxidative Coupling of Simple Arenes with Alkenes (Alkenylation of Arenes) 486

13.4 Oxidative Cross-Coupling of Simple Arenes (Atylation of Arenes) 490

13.4.1 Single-Electron Transfer Processes 490

13.4.2 Aryl C-H Activation 494

13.5 Summary 498

References 499.

Notes:

Includes bibliographical references and index.

ISBN:

9781119092520

1119092523

OCLC:

953805814