Françoise Colobert, PhD, is director of the team Syncat: Synthesis and asymmetric catalysis of the Chemistry Engineering High School ECPM at the University of Strasbourg. Her current research interests are oriented towards homogeneous catalysis, in particular C-H activation directed by sulfoxides.

Joanna Wencel-Delord, PhD, was educated in chemistry at the Ecole Nationale Supérieure de Chimie de Rennes, France. Her research focuses on the transition metal-catalyzed asymmetric C-H activation.

Foreword xi

Part I Asymmetric Activation of C(sp³)—H Bonds 1

Part I.A C(sp³)—H Bond Insertion by Metal Carbenoids and Nitrenoids 2

1 Stereoselective C—C Bond-Forming Reactions Through C(sp³)—H Bond Insertion of Metal Carbenoids 3
Aoife M. Buckley, Thomas A. Brouder, Alan Ford, and Anita R. Maguire

1.1 Introduction 3

1.2 Diazo Compounds 4

1.3 Mechanistic Understanding 5

1.4 Catalysts 7

1.4.1 Copper 7

1.4.1.1 Bisoxazoline and Schiff Base 7

1.4.2 Rhodium 8

1.4.2.1 Rhodium(II) Carboxylates 9

1.4.2.2 Rhodium(II) Carboxamidates 10

1.4.2.3 Ortho-metalated Complexes 11

1.4.3 Iridium and Ruthenium 11

1.5 Intramolecular C(sp³)—H Bond Insertion 11

1.5.1 Chemoselectivity 13

1.5.1.1 Catalyst Effects 13

1.5.1.2 Substrate Effects 14

1.5.2 Regioselectivity 16

1.5.2.1 Formation of Three-Membered Rings 17

1.5.2.2 Formation of Four-Membered Rings 18

1.5.2.3 Formation of Five-Membered Rings 20

1.5.2.4 Formation of Six-Membered Rings 20

1.5.3 Diastereoselectivity 23

1.5.3.1 Substrate Effects 23

1.5.3.2 Catalyst Effects 25

1.5.4 Enantioselectivity 25

1.6 Intermolecular C(sp³)—H Bond Insertion 30

1.6.1 Chemoselectivity 30

1.6.1.1 Diazo Compounds 32

1.6.1.2 Catalyst Effects 34

1.6.1.3 Substrate Functional Groups 35

1.6.2 Regioselectivity 36

1.6.2.1 Substrate Effects 36

1.6.2.2 Catalyst Effects 38

1.6.2.3 Diazo Compound Effects 39

1.6.3 Diastereoselectivity 39

1.6.3.1 Substrate Effects 39

1.6.3.2 Catalyst Effects 42

1.6.4 Enantioselectivity 43

1.7 Conclusion 45

References 45

2 Stereoselective C—N Bond-Forming Reactions Through C(sp³)—H Bond Insertion of Metal Nitrenoids 51
Philippe Dauban, Romain Rey-Rodriguez, and Ali Nasrallah

2.1 Introduction 51

2.2 Historical Background 52

2.2.1 Seminal Studies in Catalytic C(sp³)–H Amination 52

2.2.2 Mechanistic and Stereochemical Issues 56

2.3 Catalytic Stereoselective C(sp³)–H Amination Reactions with Iminoiodinanes 60

2.3.1 Catalytic Intermolecular Enantioselective Reactions (Chirality Only on the Metal Complex) 60

2.3.2 Catalytic Intramolecular Enantioselective Reactions 63

2.3.3 Catalytic Intermolecular Diastereoselective Reactions (Chirality on the Metal Complex and the Nitrene Precursor) 66

2.4 Catalytic Stereoselective C(sp³)–H Amination Reactions with Azides 67

2.4.1 Transition Metal-Catalyzed C(sp³)–H Amination Reactions 67

2.4.2 Enzymatic C(sp³)–H Amination Reactions 68

2.5 Catalytic Stereoselective C(sp³)–H Amination Reactions with N-(Sulfonyloxy)carbamates 70

2.6 Conclusion 72

References 72

Part I.B C(sp³)–H Activation as Stereodiscriminant Step 77

3 Enantioselective Intra- and Intermolecular Couplings 79
Qiaoqiao Teng and Wei-Liang Duan

3.1 Introduction 79

3.2 Enantioselective Intramolecular Couplings of Aliphatic Substrates 79

3.2.1 C–C Coupling 79

3.2.2 C–X Coupling 89

3.3 Enantioselective Intermolecular Couplings of Aliphatic Substrates 90

3.3.1 Pd Catalysis 91

3.3.2 Rh Catalysis 102

3.3.3 Ir Catalysis 102

3.4 Conclusion 104

References 105

4 Substrate-Controlled Transformation: Diastereoselective Functionalization 107
Sheng-Yi Yan, Bin Liu, and Bing-Feng Shi

4.1 Introduction 107

4.2 Diastereoselective Functionalizations of N-Phthaloyl-α-Amino Acids 108

4.2.1 Diastereoselective β-C(sp³)–H Functionalizations of N-Phthaloyl-α-Amino Acids 108

4.2.1.1 Bidentate Directing Group 108

4.2.1.2 Monodentate Directing Group 114

4.2.2 Diastereoselective γ-C(sp³)–H Functionalization of α-Amino Acid Derivatives 114

4.3 Diastereoselective C–H Activation Controlled by Chiral Auxiliary 116

4.4 Diastereoselective C(sp³)–H Functionalization of Conformationally Restricted Cyclic Substrates 121

4.5 Summary and Conclusions 127

References 128

Part II Stereoselective Synthesis Implying Activation of C(sp²)—H Bonds 131

5 Planar Chirality via C(sp²)–H Activation Involved in Stereodiscriminant Step 133
Qing Gu and Shu-Li You

5.1 Introduction 133

5.2 Diastereoselective Synthesis of Planar Chiral Ferrocenes 134

5.3 Enantioselective Synthesis of Planar Chiral Ferrocenes 134

5.3.1 Pd(II)-Catalyzed Direct C—H Bond Functionalization 134

5.3.2 Pd(0)-Catalyzed Direct C—H Bond Functionalization 140

5.3.3 Ir/Rh-Catalyzed Direct C—H Bond Functionalization 144

5.3.4 Au/Pt-Catalyzed Direct C—H Bond Functionalization 146

5.4 Conclusion 147

References 148

6 Axial Chirality via C(sp²)–H Activation Involved in Stereodiscriminant Step 151
Quentin Dherbassy, Joanna Wencel-Delord, and Françoise Colobert

6.1 Introduction 151

6.2 Asymmetric Coupling of Two Arenes by Oxidative Dimerization 152

6.2.1 Copper-Catalyzed Reactions 153

6.2.2 Vanadium-Catalyzed Reactions 154

6.2.3 Iron-Catalyzed Reactions 155

6.2.4 Application in the Synthesis of Natural Products 155

6.2.5 Conclusion 156

6.3 Stereoselective C–H Functionalization of Prochiral or Racemic Biaryls 158

6.3.1 Asymmetric C–H Alkylation of Naphthylpyridines 158

6.3.2 Diastereoselective C–H Functionalization Using a Chiral Directing Group 159

6.3.2.1 Sulfinyl as Chiral Directing Group 159

6.3.2.2 Phosphates as Chiral Directing Group 162

6.3.3 Enantioselective C–H Functionalization of Racemic Biaryl 163

6.3.4 Stereoselective C–H Functionalization Using a Transient Chiral Directing Group 165

6.3.5 Conclusion 167

6.4 Atroposelective Cross-Coupling of Two Moieties 167

6.4.1 Pd-Catalyzed C–H Arylation of Thiophene Derivatives 167

6.4.2 Pd-Catalyzed C–H Arylation of Biaryl Sulfoxides 169

6.4.3 Rh-Catalyzed C–H Arylation of Diazonaphthoquinones 171

6.4.4 Conclusion 172

6.5 General Conclusion 172

References 172

7 Central Chirality via Asymmetric C(sp²)–H Activation Implying Desymmetrization and Kinetic Resolution 175
Soufyan Jerhaoui, Françoise Colobert, and Joanna Wencel-Delord

7.1 Synthesis of C-Stereogenic Molecules via C(sp²)–H Functionalization 175

7.1.1 Desymmetrization 175

7.1.2 Kinetic Resolution 182

7.2 Synthesis of P-Central Chiral Molecules via C(sp²)–H Functionalization 183

7.3 Synthesis of Chiral Organosilicon Molecules via C(sp²)–H Functionalization 187

7.4 Synthesis of S-Chiral Molecules via C(sp²)–H Functionalization 189

7.5 Conclusions 190

References 191

8 Non-stereoselective C(sp²)–H Activation Followed by Selective Functionalization of Metallacyclic Intermediate 193
Xiaohong Chen, Xue Gong, Bo Wang, and Guoyong Song

8.1 Introduction 193

8.2 Intramolecular Couplings 194

8.2.1 Palladium and Nickel Catalysis 194

8.2.2 Rhodium Catalysis 196

8.2.3 Iridium Catalysis 200

8.2.4 Enantioselective Hydroacylation 203

8.3 Intermolecular Couplings 210

8.3.1 Rhodium Catalysis 210

8.3.2 Iridium Catalysis 219

8.3.3 Other Metal Catalysis 226

8.4 Conclusion 231

Acknowledgments 231

References 231

9 Diastereoselective Formation of Alkenes Through C(sp²)—H Bond Activation 239
Parthasarathy Gandeepan and Lutz Ackermann

9.1 Introduction 239

9.2 C–H Activation with Alkenes 241

9.2.1 Nondirected C–H Alkenylation 241

9.2.2 Directed C–H Alkenylation 244

9.3 C–H Activation with Alkenyl (Pseudo)halides 250

9.4 Hydroarylation 252

9.4.1 Hydroarylation of Alkynes 252

9.4.2 Hydroarylation of Allenes 257

9.5 Hydroacylation 261

9.5.1 Hydroacylation of Alkynes 261

9.5.2 Hydroacylation of Allenes 263

9.6 Conclusion 264

References 265

Index 275

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