1 Oxidative Coupling - Bonding between Two Nucleophiles 1 1.1 Introduction/General 1 1.1.1 What is Oxidative Cross-Coupling? 1 1.1.2 Why Oxidative Cross-Coupling? 1 1.1.3 How Does Oxidative Cross-CouplingWork? 3 1.

1.4 Development and Outlook 4 References 4 2 Organometals as Nucleophiles 7 2.1 Classification and Applications of Organometallic Reagents 7 2.2 Csp-M and Csp-M as Nucleophiles 8 2.2.1 Alkyne-Alkyne Oxidative Coupling 9 2.2.1.

1 Alkynyl-Si 11 2.2.1.2 Alkynyl-Sn 12 2.2.1.3 Alkynyl-B 14 2.2.

1.4 Alkynyl-Mg 17 2.2.1.5 Alkynyl-Te 19 2.2.2 Alkyne-Cyano Oxidative Coupling 22 2.3 Csp-M and Csp2-M as Nucleophiles 22 2.

4 Csp-M and Csp3-M as Nucleophiles 28 2.5 Csp2-M and Csp2-M as Nucleophiles 30 2.5.1 Homocoupling of Csp2-M 30 2.5.2 Cross-Coupling between Different Species of Csp2-M 32 2.6 Csp2-M and Csp3-M as Nucleophiles 34 2.7 Csp3-M and Csp3-M as Nucleophiles 37 2.

8 Conclusions 40 Acknowledgments 41 References 42 3 Oxidative Couplings Involving the Cleavage of C-H Bonds 45 3.1 Theoretical Understandings and Methods in C-H Bond Functionalization 45 3.1.1 Introduction 45 3.1.2 Mechanisms of C-H Cleavage by Transition Metals 47 3.1.2.

1 Oxidative Addition 49 3.1.2.2 Electrophilic Substitution 49 3.1.2.3 σ-Bond Metathesis 52 3.1.

2.4 Concerted Metalation Deprotonation (CMD) 52 3.1.2.5 1,2-Addition 55 3.1.2.6 Biomimetic C-H Oxidation 55 3.

1.2.7 Carbenoid/Nitrenoid C-H Insertion 56 3.1.3 Methods for Selective C-H Bond Functionalization 58 3.1.3.1 Directed C-H Functionalization 58 3.

1.3.2 Sterically Controlled C-H Functionalization 63 3.1.3.3 C-H Functionalization via Ionic Intermediates 63 3.1.3.

4 C-H Functionalization via Radical Intermediates 67 3.2 Oxidative Couplings between Organometals and Hydrocarbons 71 3.2.1 C(sp)-H and Organometals as Nucleophiles 71 3.2.2 Csp2-H and Organometals as Nucleophiles 73 3.2.3 Csp3-H and Organometals as Nucleophiles 93 3.

3 Oxidative Couplings between Two Hydrocarbons 95 3.3.1 C(sp)-H and C(sp)-H as Nucleophiles 95 3.3.2 C(sp)-H and C(sp2)-H as Nucleophiles 99 3.3.3 C(sp)-H and C(sp3)-H as Nucleophiles 105 3.3.

4 Csp2-H and Csp2-H as Nucleophiles 106 3.3.4.1 Oxidative Coupling between Directing-Group-Containing Arenes and Unactivated Arenes 107 3.3.4.2 Oxidative Coupling of Arenes without Directing Groups 109 3.3.

4.3 Intramolecular Oxidative Coupling of Unactivated Arenes 110 3.3.4.4 Oxidative Heck-Type Cross-Coupling 114 3.3.5 Csp2-H and Csp3-H as Nucleophiles 123 3.3.

5.1 Intramolecular Oxidative Coupling between Aromatic Csp2-H and Csp3-H 123 3.3.5.2 Intramolecular Oxidative Coupling between Alkene Csp2-H and Csp3-H 125 3.3.5.3 Intermolecular Oxidative Coupling between Csp2-H and Csp3-H 127 3.

3.6 C(sp3)-H and C(sp3)-H as Nucleophiles 128 3.4 Conclusions 130 References 130 4 Bonding Including Heteroatoms via Oxidative Coupling 139 4.1 Introduction 139 4.2 Oxidative C-O Bond Formation 140 4.2.1 C-H and O-M as Nucleophiles 140 4.2.

2 C-H and O-H as Nucleophiles 140 4.2.2.1 C(sp2, Aryl)-O Bond Formation 140 4.2.2.2 C(sp2, Heteroaryl, Alkenyl)-O Bond Formation 144 4.2.

2.3 C(sp3, Benzyl)-O Bond Formation 145 4.2.2.4 C(sp3, Alkanes with Directing Group)-O Bond Formation 145 4.2.2.5 C(sp3, Ethers, Amines, Amides, Alkanes)-O Bond Formation 148 4.

2.2.6 C(sp3, allyl)-O Bond Formation 148 4.3 Oxidative C-N Bond Formation 152 4.3.1 C(sp)-N Bond Formation 152 4.3.2 C(sp2, Arenes with Directing Group)-N Bond Formation 153 4.

3.3 C(sp2, Simple Arenes)-N Bond Formation 156 4.3.4 C(sp2, Heteroaryl)-N Bond Formation 156 4.3.5 C(sp2, Alkenyl)-N Bond Formation 159 4.3.6 C(sp3, Alkyl)-N Bond Formation 163 4.

3.7 C(sp3, Allyl)-N Bond Formation 164 4.4 Oxidative C-Halo Bond Formation 166 4.4.1 C-H and Halo-H as Nucleophiles 167 4.4.2 C-H and Halo-M as Nucleophiles 168 4.5 Oxidative C-S Bond Formation 170 4.

5.1 C(sp2)-S Bond Formation 170 4.5.2 C(sp)-S Bond Formation 171 4.6 Oxidative C-P Bond Formation 172 4.6.1 C(sp2, Aryl)-P Bond Formation 172 4.6.

2 C(sp2, Heteroaryl)-P Bond Formation 173 4.6.3 C(sp2, Alkenyl)-P Bond Formation 176 4.6.4 C(sp)-P Bond Formation 176 4.6.5 C(sp3)-P Bond Formation 176 4.7 Oxidative C-B Bond Formation 177 References 178 5 Oxidative Radical Couplings 185 5.

1 Introduction 185 5.2 Oxidative Radical C-C Couplings 185 5.2.1 Coupling of Csp3-H with Csp-H Bonds 185 5.2.2 Coupling of Csp3-H with Csp2-H Bonds 187 5.2.3 Coupling of Csp3-H with Csp3-H Bonds 200 5.

2.4 Coupling of Csp2-H with Csp2-H Bonds 204 5.3 Oxidative Radical C-C Couplings through Cascade Process 208 5.4 Oxidative Radical C-C Couplings via C-C(N) Bond Cleavage 217 References 222 Index 225.