Transition-Metal-Catalyzed C-H Functionalization of Heterocycles, 2 Volumes

Tharmalingam Punniyamurthy, PhD is Professor of Chemistry and Dean of Faculty Affairs at the Indian Institute of Technology Guwahati, India. Anil Kumar, PhD is Professor in the Department of Chemistry at the Birla Institute of Technology and Science, Pilani, India.

• ContentsList of Contributors xiii8 Functionalization of Pyridines, Quinolines, and Isoquinolines 357Jun Zhou and Bing-Feng Shi8.1 Introduction 3578.2 C2-Selective Functionalization 3588.2.1 Alkylation 3588.2.2 Arylation 3618.2.2.1 Pyridine Derivatives as Substrates 3618.2.2.2 Pyridine N-oxides as Substrates 3638.2.2.3 N-iminopyridinium Ylides as Substrates 3658.2.3 Alkenylation 3658.2.4 Acylation, Amination, and Aminomethylation 3678.3 C3-Selective Functionalization 3708.3.1 Alkylation 3708.3.2 Arylation 3718.3.3 Alkenylation 3748.3.4 Borylation 3778.4 C4-Selective Functionalization 3788.4.1 Alkylation 3788.4.2 Arylation 3808.4.3 Alkenylation 3818.4.4 Borylation 3828.5 C8-Selective Functionalization 3828.6 Summary and Conclusions 3879 Transition Metal-Catalyzed C-H Bond Functionalization of Diazines and Their Benzo Derivatives 393Christian Bruneau and Rafael Gramage-Doria9.1 Introduction 3939.2 Carbon-carbon Bond Formation 3949.2.1 C-H Bond (Hetero)arylations 3949.2.2 C–H Bond Olefinations 4069.2.3 C–H Bond Alkylations 4159.2.4 C–H Bond Alkynylations 4189.2.5 C–H Bond Carboxylations 4199.3 Carbon-nitrogen Bond Formation 4209.4 Carbon-oxygen Bond Formation 4249.5 Carbon-sulfur Bond Formation 4249.6 Carbon-boron Bond Formation 4259.7 Carbon-silicon Bond Formation 4259.8 Carbon-halogen Bond Formation 4279.9 Conclusions 428Acknowledgments 42910 Functionalization of Chromenes and Their Derivatives 435Laura Cunningham, Sundaravel Vivek Kumar, and Patrick J. Guiry10.1 Introduction 43510.2 2 H-Chromenes 43510.3 2 H-Chromene-ones (Coumarins) 43710.3.1 C3-Selective Functionalization 43710.3.1.1 Alkenylation 43710.3.1.2 Arylation 43810.3.1.3 Other 44110.3.1.4 Annulation/Cyclization 44210.3.2 C4–H Selective Functionalization 44910.3.3 C5-Selective Functionalization 45610.4 4 H-Chromene 45910.5 4 H-Chromenones (Chromones) 46210.5.1 C2-Selective C–H Activation 46210.5.2 C3-Selective C–H Activation 46310.5.3 C5-Selective C–H Activation 46810.5.3.1 Alkenylation 46810.5.3.2 Alkylation 47110.5.3.3 (Hetero)arylation 47310.5.3.4 Amination/Amidation 47410.5.3.5 Others 47710.5.4 C6-Selective C–H Activation 47810.5.5 Conclusions 47811 Transition Metal-Catalyzed C–H Functionalization of Imidazo-fused Heterocycles 485Rajeev Sakhuja and Anil Kumar11.1 Introduction 48511.2 C–C Bond Formation 48611.2.1 Alkylation 48611.2.1.1 Fluoro Alkylation 48611.2.1.2 Alkoxycarbonyl Alkylation 48811.2.1.3 Aryl/heteroaryl Alkylation 48911.2.1.4 Amino Alkylation 49311.2.1.5 Sulfonyl/Carbonyl/Cyano Alkylation 49611.2.2 Alkenylation/Alkynylation/Allenylation 49811.2.3 Cyanation/Carbonylation 50311.2.4 Arylation/Heteroarylation 50911.3 C–S/Se Bond Formation 52511.4 C–N Bond Formation 53211.5 C–P Bond Formation 53311.6 C–Si Bond Formation 53511.7 Conclusions 535Acknowledgments 53612 Dehydrogenative Annulation of Heterocycles: Synthesis of Fused Heterocycles 543Neha Jha and Manmohan Kapur12.1 Dehydrogenative Coupling: An Overview 54312.2 Importance of Heterocycles and Their Fused Congeners 54512.3 Metal-Catalyzed Dehydrogenative-coupling Reactions: Formation of C–Z Bonds 54612.3.1 C–C Bond Formation 54612.3.1.1 Synthesis of Large-sized Molecules: COTs 54912.3.2 Formation of C–N Bonds 55012.3.3 Formation of C–B Bonds 55712.4 Conclusions 56213 C–H Functionalization of Saturated Heterocycles Beyond the C2 Position 567Amalia-Sofia Piticari, Natalia Larionova, and James A. Bull13.1 Introduction 56713.2 Heterocycle Functionalization with a C2 Directing Group 56713.2.1 Carboxylic Acid-Linked C2 Directing Groups 56713.2.2 Applications of N-Heterocycle Functionalization with C2 Directing Groups 58013.3 Heterocycle Functionalization with C3 Directing Groups 58613.3.1 Carboxylic Acid-Linked C3 Directing Groups 58613.3.2 Amine-Linked C3 Directing Groups 59013.3.3 Alcohol-Linked C3 Directing Groups 59213.4 Heterocycle Functionalization with a C4 Directing Group 59413.5 Transannular Heterocycle Functionalization with N-linked Directing Groups 59813.6 Conclusions 60314 Asymmetric Functionalization of C–H Bonds in Heterocycles 609Olena Kuleshova and Laurean Ilies14.1 Introduction 60914.2 Enantioselective C–H Activation 60914.2.1 Activation of C(sp2)–H Bonds 60914.2.2 Activation of C(sp3)–H Bonds 61114.3 C–H Activation Followed by Enantioselective Functionalization 61514.3.1 Intramolecular Coupling 61514.3.1.1 Indoles and Pyrroles as Coupling Partners 61514.3.1.2 Imidazoles and Benzoimidazoles as Coupling Partners 61814.3.1.3 Pyridines and Pyridones as Coupling Partners 61814.3.2 Intermolecular Coupling 61914.3.2.1 Directing-Group-Free C–H Functionalization 61914.3.2.2 Functionalization Assisted by a Directing Group at the C3 Site 62114.3.2.3 Functionalization Assisted by a Directing Group at the N-1 Site 62314.3.3 Atropo-enantioselective Synthesis of Heterobiaryls 62414.4 Conclusions and Perspectives 62715 Transition Metal-Catalyzed C–H Functionalization of Nucleoside Bases 631Yong Liang and Stanislaw F. Wnuk15.1 Introduction 63115.2 Direct Functionalization of the C5-H Bond in Uracil Nucleosides 63215.2.1 Cross-Dehydrogenative Alkenylation at the C5 Position 63215.2.2 Direct C–H Arylation at the C5 Position 63415.2.3 Direct C–H Alkylation at the C5 Position 63515.2.4 Miscellaneous Direct C–H Functionalizations 63615.3 Direct Functionalization of C6-H Bond in Uracil 63715.3.1 Stepwise C6-H Functionalization of Pyrimidine Nucleoside via Lithiation and Alkylation 63715.3.2 Direct C6-H Functionalization of the Uracil Base 63715.3.2.1 Functionalization with Aryl Halides 63715.3.2.2 Cross-Dehydrogenative Functionalization with Arenes 63815.3.2.3 Functionalization with Aryl Boronic Acid 63915.3.2.4 Intramolecular C6-H Functionalization of Uracil Derivatives 63915.4 Inverted C–H Functionalization of Uracil Nucleosides 64015.4.1 Inverted C5-H Functionalization of Uracil Nucleosides 64015.4.2 Inverted C6-H Functionalization of Uracil 64115.5 Direct C2-H Functionalization of Adenosine 64115.6 Direct C6-H Functionalization of Purine Nucleoside 64215.6.1 Direct C6-H Alkylation 64215.6.1.1 With Cycloalkanes 64215.6.1.2 With Boronic Acid 64315.6.1.3 With Alkyltrifluoroborate 64315.6.1.4 With Alkyl Carboxylic Acid 64315.6.1.5 With tert-Alkyl Oxalate Salts 64415.6.2 Direct C6-H Arylation 64415.6.3 Other Direct C6-H Functionalization 64515.7 Direct Activation of C8-H Bond in Purine and Purine Nucleosides 64515.7.1 Cross-Coupling of Adenine Nucleosides with Aryl Halides 64515.7.2 Cross-Coupling of Inosine and Guanine Nucleosides with Aryl Halides 64715.7.3 Cross-Coupling of Adenine Nucleosides with Alkanes 64815.7.4 Miscellaneous Functionalization of Adenosine-related Substrates 64915.8 Conclusions 65016 C–H Activation for the Synthesis of C1-(hetero)aryl Glycosides 657Morgane de Robichon, Juba Ghouilem, Angélique Ferry, and Samir Messaoudi16.1 General Introduction 65716.2 Classical Methods to Prepare C-aryl Glycosides 65716.3 Directed C-H Activation Approach 65816.3.a Directed Csp2-Csp2 Bond Formation 65916.3.a.1 Directing Group Attached to the Aryl Partner 65916.3.a.2 Directing Group Attached to the Sugar Nucleus 66116.3.b Directed Csp2-Csp3 Bond Formation 66216.3.b.1 The Directing Group (DG) Attached to the Coupling Partner 66216.3.b.2 The Directing Group Attached to the Sugar Nucleus 67516.4 Conclusions and Perspectives 67917 Late-stage C–H Functionalization: Synthesis of Natural Products and Pharmaceuticals 683Harshita Shet and Anant R. Kapdi17.1 Introduction 68317.2 Synthesis of (±)-Ibogamine 68417.3 Synthesis of YD-3 and YC-1 (C–H Arylation of Indazoles) 68517.4 Synthesis of Complanadine A 68517.5 Synthesis of Diptoindonesin G (C–H Arylation of Benzofuran) 68617.6 Synthesis of Dragmacidin D (C–H Arylation of Indoles at the C3 Position) 68717.7 Synthesis of Celecoxib (C–H Arylation of Pyrazoles) 68817.8 Synthesis of Aspidospermidine 68917.9 Synthesis of Pipercyclobutanamide A 69017.10 Synthesis of Nigellidine Hydrobromide 69117.11 Synthesis of (+)-Linoxepin 69117.12 Synthesis of (±)-Rhazinal 69217.13 Synthesis of Podophyllotoxin (C–H Arylation) 69317.14 Synthesis of (±)-Rhazinilam 69417.15 Synthesis of Aeruginosins (sp3 C–H Alkenylation and Arylation) 69417.16 Synthesis of Gamendazole 69617.17 Synthesis of Beclabuvir (BMS-791325) 69717.18 Conclusions 69818 Late-stage Functionalization of Pharmaceuticals, Agrochemicals, and Natural Products 703François Richard, Elias Selmi-Higashi, and Stellios Arseniyadis18.1 C–H Methylation and Alkylation 70418.2 C–H Arylation and Olefination 70518.3 Formation of Other C−C Bonds 71118.4 C–H Hydroxylation 71418.5 C–H Amination 71518.6 C–H Trifluoromethylation 71618.7 C–H Difluoromethylation 71618.8 C–H Fluorination 71818.9 C–H Silylation 71818.10 C–H Phosphorylation 71918.11 C–H Deuteration and Tritiation 72018.12 Conclusions 723Index 727Brief ContentsVolume 1:List of Contributors xiiiPreface xvii1 Historical Perspective and Mechanistic Aspects of C–H Bond Functionalization 1Tariq M. Bhatti, Eileen Yasmin, Akshai Kumar, and Alan S. Goldman2 Recent Advances in C–H Functionalization of Five–Membered Heterocycles with Single Heteroatoms 61B. Prabagar and Zhuangzhi Shi3 Functionalization of Five-membered Heterocycles with Two Heteroatoms 109Jung Min Joo4 Transition Metal-Catalyzed C–H Functionalization of Indole Benzenoid Ring 155Vikash Kumar, Rajaram Maayuri, Lusina Mantry, and Parthasarathy Gandeepan5 Transition Metal-Catalyzed C2 and C3 Functionalization of Indoles 193Pinki Sihag, Meledath Sudhakaran Keerthana, and Masilamani Jeganmohan6 C(sp2)–H Functionalization of Indolines at the C7-Position 251Neeraj Kumar Mishra and In Su Kim7 Transition Metal-Catalyzed C–H Functionalization of Benzofused Azoles with Two or More Heteroatoms 319Tanumay Sarkar, Subhradeep Kar, Prabhat Kumar Maharana, Tariq. A. Shah, and Tharmalingam PunniyamurthyVolume 2:List of Contributors xiii8 Functionalization of Pyridines, Quinolines, and Isoquinolines 357Jun Zhou and Bing-Feng Shi9 Transition Metal-Catalyzed C-H Bond Functionalization of Diazines and Their Benzo Derivatives 393Christian Bruneau and Rafael Gramage-Doria10 Functionalization of Chromenes and Their Derivatives 435Laura Cunningham, Sundaravel Vivek Kumar, and Patrick J. Guiry11 Transition Metal-Catalyzed C–H Functionalization of Imidazo-fused Heterocycles 485Rajeev Sakhuja and Anil Kumar12 Dehydrogenative Annulation of Heterocycles: Synthesis of Fused Heterocycles 543Neha Jha and Manmohan Kapur13 C–H Functionalization of Saturated Heterocycles Beyond the C2 Position 567Amalia-Sofia Piticari, Natalia Larionova, and James A. Bull14 Asymmetric Functionalization of C–H Bonds in Heterocycles 609Olena Kuleshova and Laurean Ilies15 Transition Metal-Catalyzed C–H Functionalization of Nucleoside Bases 631Yong Liang and Stanislaw F. Wnuk16 C–H Activation for the Synthesis of C1-(hetero)aryl Glycosides 657Morgane de Robichon, Juba Ghouilem, Angélique Ferry, and Samir Messaoudi17 Late-stage C–H Functionalization: Synthesis of Natural Products and Pharmaceuticals 683Harshita Shet and Anant R. Kapdi18 Late-stage Functionalization of Pharmaceuticals, Agrochemicals, and Natural Products 703François Richard, Elias Selmi-Higashi, and Stellios ArseniyadisIndex 727