Preface xiii 1 History of Directed C--H Bond Activation and its Discovery 1 Susmita Mondal, Sumit Ghosh, Asim Kumar Ghosh, and Alakananda Hajra 1.1 Introduction 1 1.2 Importance of C--H Activation 2 1.3 Early Discoveries in Stoichiometric Metal-promoted Proximal C--H Bond Functionalization 3 1.4 Directing Group-assisted Catalytic Proximal C--H Bond Functionalization 3 1.4.1 In-built Functional-Group-directed Proximal C--H Bond Functionalization 3 1.4.
2 Removable Directing Group-assisted Proximal C--H Bond Functionalization 11 1.4.2.1 Pre-installed and Post-removable Directing Groups-assisted C--H Bond Activation 11 1.4.2.2 Traceless Directing Group-assisted C--H Bond Functionalization 13 1.4.
2.3 Transient Directing Group (TDG)-assisted C--H Bond Activation 15 1.5 Directed Distal C--H Bond Functionalization 17 1.5.1 meta-C--H Bond Functionalization 17 1.5.2 para-C--H Bond Functionalization 20 1.5.
3 Remote C--H Functionalization 24 1.6 Conclusions 28 Acknowledgments 29 References 29 2 Pd-catalyzed In-built Functional Group-directed C--H Functionalization 37 Ananya Dutta and Masilamani Jeganmohan 2.1 Introduction 37 2.2 In-built Nitrogen Atom in a Heterocycle as the Efficient Directing Group 39 2.3 Aliphatic Amines as the In-built Functional Group 39 2.3.1 Pd-catalyzed Amine-directed Intramolecular C(sp3)--H Amination 40 2.3.
2 Pd-catalyzed In-built Amine-directed C--H Arylation 40 2.3.3 Pd-catalyzed Amine-directed C--H Acetoxylation 44 2.3.4 Pd-catalyzed Amine-directed Alkenylation Reaction 45 2.3.5 Amine Group-directed Carbonylation Reactions 47 2.4 Carboxylic Acids as the In-built Functional Group in C--H Activation 48 2.
4.1 Pd-catalyzed C(sp2)--H Bond Functionalization of Benzoic and Phenyl Acetic Acids 50 2.4.1.1 Pd-catalyzed Carboxylate Group-directed C(sp2)--H Bond Arylation of Benzoic Acids 50 2.4.1.2 Pd-catalyzed Carboxylate Group-directed Benzolactone and Isocoumarin Formation Using Benzoic Acids 50 2.
4.1.3 Pd-catalyzed Carboxylate-assisted Halogenation, Amidation, Carboxylation, and Acylation Reaction of Benzoic Acids 53 2.4.1.4 Pd-catalyzed Carboxylate-assisted C(sp2)--H Bond Arylation of Phenyl Acetic Acids 55 2.4.1.
5 Ligand-assisted Pd-catalyzed Olefination of Substituted Phenyl Acetic Acids 57 2.4.1.6 Pd-catalyzed ortho-C(sp2)--H Functionalizations of Phenyl Acetic Acids 57 2.4.2 Benzylic C(sp3)--H Activation of Carboxylate Directing Group 60 2.4.2.
1 External ligand-assisted Benzylic C(sp3)--H Activation of Carboxylate Motifs 60 2.4.3 Pd-catalyzed C(sp3)--H Activation of Aliphatic Acids Assisted by In-built Carboxylate Group 61 2.4.3.1 Pd-catalyzed Carboxylate-assisted Arylation of Proximal Aliphatic C(sp3)--H Bonds 61 2.4.3.
2 Pd-catalyzed External Ligand-assisted Lactonization of Proximal C(sp3)--H Bonds 63 2.4.3.3 Pd-catalyzed Carboxylate-assisted β-C(sp3)--H Acetoxylation 63 2.4.3.4 Pd-catalyzed β-C(sp3)--H Alkynylation and Deuteration of Free Carboxylic Acids 65 2.4.
3.5 Pd-catalyzed Ligand-assisted Distal C(sp3)--H Bond Arylation 66 2.4.3.6 Pd-catalyzed Ligand-assisted Distal C(sp3)--H Bond Lactonization 66 2.4.3.7 Pd-catalyzed Enantioselective Carboxylate-directed C(sp3)--H Activation 68 2.
5 Aldehyde as the In-built Functional Group in C--H Activation 69 2.5.1 Pd-catalyzed C(sp2)--H Functionalization of Free Aldehydes 71 2.6 Sulfonic Acid as the In-built Functional Group in C--H Activation 71 2.6.1 Pd-catalyzed C(sp2)--H Functionalization of Free Sulfonic Acids 71 2.7 Alcohols as the In-built Functional Group in C--H Activation 72 2.7.
1 Phenethyl Alcohol as the In-built Functional Group 72 2.7.2 Phenol as the In-built Functional Group 73 2.7.3 Hydroxyl Moiety of Salicylaldehyde as the In-built Functional Group 74 2.7.4 Miscellaneous Examples of Free Alcohol as the In-built Functional Group 74 2.8 Conclusion 75 References 76 3 Traceless Directing Group in C--H Bond Functionalization 85 Shuvojit Haldar and Debasis Banerjee 3.
1 Introduction 85 3.2 Classification of the Traceless Groups 87 3.3 Carbonyl Group as a Traceless Directing Group 87 3.3.1 Carboxylic Acid as a Traceless Directing Group for Various Organic Transformations 87 3.3.1.1 Carboxylic Acid as a Traceless Directing Group Toward Biaryl Synthesis 87 3.
3.1.2 Carboxylic Acid as a Traceless Directing Group: Alkylation of Indole 90 3.3.1.3 Carboxylic Acid as a Traceless Directing Group in Alkylation/Alkenylation 93 3.3.2 Aldehyde and Ketone as a Traceless Directing Group 95 3.
3.3 Ester as a Traceless Directing Group 96 3.3.4 Amide as a Traceless Directing Group 96 3.3.5 CO2 as a Traceless Directing Group in C--H Bond Activation 97 3.3.6 tert-Butoxycarbonyl (BOC) Group as a Traceless Directing Group 97 3.
4 Nitrogen-containing Functional Groups as a Traceless Directing Group 98 3.4.1 Amine as a Traceless Directing Group 98 3.4.2 Hydrazone as a Traceless Directing Group 99 3.4.3 N-O Group as a Traceless Directing Group 100 3.4.
4 Alkene-tethered Aldoxime as a Traceless Directing Group 101 3.5 Miscellaneous Groups as a Traceless Directing Group 102 3.5.1 ((Pinacolato)boron (Bpin)) Group as a Traceless Directing Group 102 3.5.2 Acetal as a Traceless Directing Group 102 3.5.3 Sulfur-based Group as a Traceless Directing Group 103 3.
5.4 Silicon Group as a Traceless Directing Group 103 3.5.5 Halides as a Traceless Directing Group 104 3.6 Conclusions 106 Acknowledgments 106 References 106 4 Removable Directing Group in Proximal C--H Functionalization 111 Vikash Kumar, Malati Das, Sivakumar Sudharsan, and Parthasarathy Gandeepan 4.1 Introduction 111 4.2 Removable Directing Groups 112 4.2.
1 C--H Functionalization of Amino Compounds 112 4.2.2 C--H Functionalization of Hydroxyl Compounds 116 4.2.3 C--H Functionalization of Aldehyde and Ketone Compounds 119 4.2.4 C--H Functionalization of Carboxylic Acids 123 4.2.
5 C--H Functionalization of Sulfonic Acid 128 4.2.6 C--H Functionalization of Heterocycles 131 4.2.7 Silicon Tethers for C--H Functionalization 135 4.3 Summary and Conclusions 137 References 138 5 Removable Template-assisted Transition Metal-catalyzed Distal C--H Functionalization 165 Ke Yang, Dan Yuan, Faith Herington, and Haibo Ge 5.1 Introduction 165 5.2 Distal C(sp2)--H Bond Functionalization 166 5.
2.1 Distal C(sp2)--H Functionalization of Arylalkyl and Aryl Acid Derivatives 166 5.2.2 Distal C(sp2)--H Functionalization of Arylalkyl and Aryl Amines 173 5.2.3 Distal C(sp2)--H Functionalization of Arylalkyl Alcohols and Phenols 178 5.2.4 Distal C(sp2)--H Functionalization of Arylalkyl Silanes 181 5.
3 Distal C(sp3)--H Bond Functionalization 184 5.3.1 γ-C(sp3)--H Bond Functionalization of Carboxylic Acids 184 5.3.2 γ-C(sp3)--H Bond Functionalization of Aliphatic Ketones 190 5.3.3 δ-C(sp3)--H Bond Functionalization of Aliphatic Amines 192 5.4 Conclusions 195 Funding 196 References 196 6 Non-covalent Template-assisted C--H Bond Functionalization 203 Yoichiro Kuninobu 6.
1 Introduction 203 6.2 Control of Site Selectivity 205 6.2.1 C(sp2)--H Transformations 205 6.2.1.1 Controlled by Hydrogen Bond 205 6.2.
1.2 Controlled by Lewis Acid-Base Interaction 213 6.2.1.3 Controlled by Electrostatic Interaction 218 6.2.1.4 Controlled by Other Non-covalent Interactions 221 6.
2.2 C(sp3)--H Transformations 226 6.2.2.1 Controlled by Hydrogen Bond 226 6.2.2.2 Controlled by Electrostatic Interaction 228 6.
2.2.3 Controlled by Other Non-covalent Interactions 230 6.3 Acceleration of Reactions and Substrate and Functional Group Specificities 230 6.4 Summary and Conclusions 235 References 236 7 Pd/Norbornene (NBE) Cooperative Catalysis in C--H Bond Activation 241 Zhibo Yan and Zhe Dong 7.1 Introduction 241 7.2 The Early Organometallic Study and Reaction Discovery 242 7.2.
1 The Stoichiometric Organometallic Study 242 7.2.2 The Initial Reaction Discovery by Catellani 246 7.3 Pd(0)/Pd(II)/Pd(IV) Catalytic Cycle: A Series of Chemoselectivity Puzzle 248 7.3.1 The S N -2-type Oxidative Addition vs Concerted Oxidative Addition: Electrophile Scope 250 7.3.2 Migratory Insertion vs β-carbon Elimination: Norbornene Modification 253 7.
4 Palladium(II)-initiated Palladium/Norbornene Catalysis 254 7.4.1 N--H Bond-initiate Palladium/Norbornene Catalysis 255 7.4.2 C--H Bond-initiated Palladium/Norbornene Catalysis 258 7.4.2.1 Directed C--H Bond Activation 258 7.
4.2.2 Non-directed C--H Bond Activation 268 7.5 Summary and Conclusions 271 References 271 8 Transient Directing Groups in C--H Bond Functionalization 277 Tsz-Kan Ma, Hannan M. Seyal, and James A. Bull 8.1 Introduction 277 8.1.
1 The Concept of Transient Directing Groups for C--H Functionalization 277 8.1.2 Early Developments Using Stoichiometric Imine to Direct C--H Functionalization 279 8.2 Transient C(sp3)--H Functionalization 282 8.2.1 C(sp3)--H Functionalization of Aldehydes 282 8.2.2 C(sp3)--H Functionalization of Ketones 287 8.
2.3.