Oxidation of C-H Bonds

Wenjun Lu, D.Eng., is a Professor of Organic Chemistry at Shanghai Jiao Tong University. Lihong Zhou, PhD, is a Research Associate at Shanghai Jiao Tong University.

Preface xi

1 Introduction 1

1.1 What Is Oxidation of C—H Bonds? 1

1.2 Chemical Synthesis and Oxidation of C—H Bonds 2

1.3 C—H Bonds 6

1.4 Concepts in This Book 15

References 17

2 Oxidation of Methane 19

2.1 Methane 19

2.2 Methyl sp³ C—H Bond 20

2.3 Oxidations of Methyl sp³ C—H Bond 21

2.4 Summary 35

References 36

3 Oxidation of Alkyl sp³ C—H Bond 39

3.1 Alkane 39

3.2 Alkyl sp³ C—H Bonds 40

3.3 Oxidations of Alkyl sp³ C—H Bond 42

3.4 Summary 61

References 62

4 Oxidation of Alkyl sp³ C—H Bond Assisted by Directing Group 65

4.1 Directing Group 65

4.2 Alkyl sp³ C—H Bonds with Directing Groups 66

4.3 Directed Oxidations of Alkyl sp³ C—H Bond 67

4.4 Summary 97

References 97

5 Oxidation of Alkyl sp³ C—H Bond Adjacent to Unsaturated Carbon Atom 101

5.1 Alkyl α-sp³ C—H Bond 101

5.2 Alkyl sp³ C—H Bonds Adjacent to Unsaturated Carbon Atoms 102

5.3 Oxidations of Alkyl sp³ C—H Bond Adjacent to Unsaturated Carbon Atom 103

5.4 Summary 138

References 138

6 Oxidation of Alkyl sp³ C—H Bond Adjacent to Heteroatom 143

6.1 Alkyl sp³ C—H Bonds Adjacent to Heteroatoms 143

6.2 Oxidations of Alkyl sp³ C—H Bond Adjacent to Heteroatom 144

6.3 Summary 166

References 167

7 Oxidation of Alkenyl or Carbonyl sp² C—H Bond 171

7.1 Alkenyl and Carbonyl sp² C—H Bonds 171

7.2 Oxidations of Alkenyl and Carbonyl sp² C—H Bonds 172

8 Oxidation of Alkynyl spC—H Bond 209

8.1 spC—H Bonds 209

8.2 Oxidations of spC—H Bond 210

8.3 Summary 232

References 232

9 Oxidation of Benzene 235

9.1 Introduction 235

9.2 Oxidations of Phenyl sp2 C—H Bond 237

9.3 Summary 277

References 279

10 Oxidation of Aryl sp² C—H Bond on Substituted Benzene 283

10.1 Introduction 283

10.2 Formation of C—C Bond 284

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

10.7 Summary 331

References 333

11 Oxidation of Aryl sp² C—H Bond Assisted by Directing Group 337

11.1 Introduction 337

11.2 Formation of C—C Bond 337

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

11.7 Summary 424

References 426

12 Oxidation of Aryl sp² C—H Bond on Heteroarene or Perfluoroarene 433

12.1 Introduction 433

12.2 Formation of C—C Bond 434

12.3 Formation of C—N Bond 459

12.4 Formation of C—O Bond 461

12.5 Formation of C—Halogen Bond 462

12.6 Cross-Coupling of Dual Aryl sp² C—H Bonds on Directing-Group-Containing Arenes, Heteroarenes, or
Polyfluoroarenes 468

12.7 Summary 477

References 478

13 Oxidative Cross-Coupling of Aryl sp² C—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 (Arylation of Arenes) 490

13.5 Summary 498

References 499

Index 501