Palladium and Norbornene Cooperative Catalysis

Preface xiii

1 The Palladium/Norbornene-Catalyzed Annulation Chemistry: Rapid Access to Diverse Ring Structures 1
Mark Lautens and Xavier Abel-Snape

1.1 Introduction 1

1.2 Intramolecular Cyclizations 3

1.3 Intermolecular Cyclizations Following Intermolecular Ortho Functionalization 21

1.4 Cyclizations with Three-Membered Heterocycles as Both the Electrophile and Terminating Reagent 22

1.5 Norbornene/Norbornadiene-Integrated Cyclizations 25

1.6 One-Pot Postcatalytic Intramolecular Cyclizations 29

1.7 Summary 32

2 Diverse Ipso Arene Functionalization by the Palladium/Norbornene Cooperative Catalysis 45
Bo-Sheng Zhang and Yong-Min Liang

2.1 Introduction 45

2.2 Ipso Functionalization Reaction in the Pd/NBE Catalytic Cycle 46

2.3 Type of Ipso Functionalization Reactions 52

2.4 Prospects and Challenges of Ipso Functionalization 80

3 Diverse Ortho C—H Functionalization by the Palladium/Norbornene Cooperative Catalysis 89
Xin Liu and Guangbin Dong

3.1 Introduction 89

3.2 Carbon-Electrophile 91

3.3 Nitrogen-Electrophile 112

3.4 Sulfur-Electrophile 116

3.5 Oxygen-Electrophile 117

3.6 Conclusion and Outlook 119

4 Asymmetric Palladium/Norbornene Cooperative Catalysis 129
Shuming Zhan and Zhenhua Gu

4.1 Introduction 129

4.2 Stereochemistry Controlled by the Substrate 131

4.3 Catalytic Asymmetric Transformations Controlled by Chiral Ligands 138

4.4 Catalytic Asymmetric Transformation Controlled by Chiral Norbornenes 142

4.5 Summary and Outlook 152

5 Pd(II)-Initiated Palladium/Norbornene Cooperative Catalysis 157
Hong-Gang Cheng, Kevin Wu, Qianghui Zhou, and Jin-Quan Yu

5.1 Introduction 157

5.2 Pd/NBE-catalyzed C–H Functionalization of NH-containing Heteroarenes 159

5.3 Directing Group-Enabled meta-C–H Functionalization of Arenes 167

5.4 Directing Group-Free Mono- and Difunctionalization of (Hetero)Arenes 179

5.5 Template-Enabled Remote C–H Functionalization 183

5.6 Enantioselective Remote C–H Functionalization 184

5.7 Borono-Catellani Reactions 188

5.8 Conclusion and Outlook 190

6 Functionalization of Heteroarenes by the Palladium/Norbornene Cooperative Catalysis 199
Jung Min Joo

6.1 Introduction 199

6.2 Pd/NBE Reactions of Five-Membered Haloheteroarenes 200

6.3 Pd/NBE Reactions of Six-Membered Haloheteroarenes 206

6.4 Pd/NBE Reactions of Parent Heteroarenes 214

6.5 Conclusion 219

7 Addressing the Substrate Limitation in the Palladium/Norbornene Cooperative Catalysis 225
Zhao Wu

7.1 Introduction 225

7.2 Ortho Constraint 227

7.3 Meta Constraint 237

7.4 Aryl Iodide Constraint 243

7.5 Beyond Aromatic Substrates 251

7.6 Conclusions and Outlook 260

8 Application of the Palladium/Norbornene Cooperative Catalysis to Synthesis of Natural Products and Materials 265
Jianchun Wang

8.1 Applications in Synthesis of Natural Products and Drugs 265

8.2 Applications in Synthesis of Organic Aromatic Materials 284

8.3 Summary 290

References 291

Index 295