CO2 as a Building Block in Organic Synthesis

A guide to the fascinating application of CO2 as a building block in organic synthesis This important book explores modern organic synthesis’ use of the cheap, non-toxic and abundant chemical CO2as an attractive C1 building block. With contributions from an international panel of experts, CO2 as a Building Block in Organic Synthesis offers a review of the most important reactions which use CO2 as a building block in organic synthesis. The contributors examine a wide-range of CO2 reactions including methylation reactions, CH bond functionalization, carboxylation, cyclic carbonate synthesis, multicomponent reactions, and many more. The book reviews the most recent developments in the field and also: Presents the most important reactions like CH-bond functionalization, carboxylation, carbonate synthesis and many more Contains contributions from an international panel of experts Offers a comprehensive resource for academics and professionals in the field Written for organic chemists, chemists working with or on organometallics, catalytic chemists, pharmaceutical chemists, and chemists in industry, CO2 as Building Block in Organic Synthesis contains an analysis of the most important reactions which use CO2 as an effective building block in organic synthesis.

Table of Contents:
1 Photochemical and Substrate‐Driven CO2 Conversion 1 Bart Limburg, Cristina Maquilon, and Arjan W. Kleij 1.1 Introduction 1 1.2 Iodine Activation of (Homo)Allylic Substrates 3 1.3 Substrate Activation Via Radical Addition/Photochemical Oxidation Processes 9 1.4 Substrate‐Induced Activation of Oxiranes 12 1.5 Substrate‐Involved Activation of Oxetanes and Azetidines 21 1.6 Concluding Remarks 21 References 22 2 C–H Carboxylations with CO2 29 Uttam Dhawa, Isaac Choi, and Lutz Ackermann 2.1 Introduction 29 2.2 Transition‐Metal‐Catalyzed C–H Carboxylation 30 2.2.1 Copper‐Catalyzed C–H Carboxylation 30 2.2.2 Cobalt‐Catalyzed C–H Carboxylation 36 2.2.3 Nickel‐Catalyzed C–H Carboxylation 36 2.2.4 Molybdenum‐Catalyzed C–H Carboxylation 38 2.2.5 Ruthenium‐Catalyzed C–H Carboxylation 38 2.2.6 Rhodium‐Catalyzed C–H Carboxylation 39 2.2.7 Palladium‐Catalyzed C–H Carboxylation 41 2.2.8 Silver‐Catalyzed C–H Carboxylation 42 2.2.9 Iridium‐Catalyzed C–H Carboxylation 45 2.2.10 Gold‐Catalyzed C–H Carboxylation 45 2.2.11 Neodymium‐Catalyzed C–H Carboxylation 45 2.3 Metal‐Free C–H Carboxylation 46 2.3.1 Base‐Mediated C–H Carboxylation 46 2.3.2 Electro‐Catalyzed C–H Carboxylation 49 2.3.3 Lewis Acid‐Mediated Carboxylation 49 2.3.4 Light‐Driven Carboxylation 50 2.4 CO2 Carboxylation Promoted by Transition Metal Complexes 52 2.5 Conclusions 53 References 53 3 Transition‐Metal‐Catalyzed C–H Carboxylation 59 Joaquim Caner and Nobuharu Iwasawa 3.1 Introduction 59 3.2 Direct C–H Carboxylation of Electron‐Deficient Arenes and (Hetero) Arenes Catalyzed by Basic Complexes 59 3.3 Direct Carboxylation of Inert Csp2─H Bonds 66 3.3.1 Rhodium‐Catalyzed C–H Carboxylation Reactions 66 3.3.2 Palladium‐Catalyzed C–H Carboxylation Reactions 76 3.4 Direct Carboxylation of Csp3─H Bonds 85 3.5 Summary and Outlook 89 References 90 4 Fixation of CO2 in Organic Molecules with Heterogeneous Catalysts 95 Dongcheng He, Hongli Wang, and Feng Shi 4.1 Introduction 95 4.2 CO2 Cycloaddition to Epoxide 96 4.2.1 Oxides 96 4.2.2 Zeolite Catalysts 97 4.2.3 Supported Nanoparticle and Lewis Acid Catalysts 98 4.2.4 Carbon and Its Derivatives 99 4.2.5 Salen, Porphyrin, and Phthalocyanine Catalyst 101 4.2.6 Ionic Liquid Catalyst 103 4.2.7 Metal−Organic Framework (MOF) Catalyst 108 4.2.8 Bifunctional Catalyst 112 4.2.9 Other Catalysts 120 4.3 Reactions of Aziridines and CO2 120 4.4 Reactions of Polyalcohols/Olefins and CO2 121 4.5 Reaction of Propargyl Alcohols/Propargyl Amines and CO2 124 4.6 Reactions of Terminal Alkynes and CO2 125 4.7 Formylation of Amines and CO2 127 4.8 Methylation of Amines and CO2 130 4.9 Other Reactions of Amines and CO2131 4.10 Hydroformylation of CO2 and Olefins into Alcohols 133 4.11 Reactions of Aromatic Halides and CO2 134 4.12 Reactions of 2‐Aminobenzonitriles and CO2 136 4.13 Conclusions 137 References 138 5 CO2 Fixation into Organic Molecules via Carbon–Heteroatom Bond Formation 155 Yu‐Nong Li, Hong‐Ru Li and Liang‐Nian He 5.1 Introduction 155 5.2 CO2 Conversion with C─N Bond Formation 157 5.2.1 Synthesis of Oxazolidinones 157 5.2.1.1 Oxazolidinone Synthesis from Aziridine and CO2 158 5.2.1.2 Oxazolidinone Synthesis from Olefin, a Nitrogen Source, and CO2 163 5.2.1.3 Oxazolidinone Synthesis from Amino Alcohols and CO2 164 5.2.1.4 Oxazolidinone Synthesis from Carboxylative Cyclization of Propargyl Amines with CO2 165 5.2.1.5 Oxazolidinone Synthesis from Propargyl Alcohol, Aliphatic Amines/2‐Aminoethanols, and CO2 167 5.2.1.6 Photoinduced Radical‐Initiated Carboxylative Cyclization of Allyl Amines with CO2 170 5.2.2 Synthesis of Isocyanates and Linear Carbamates 172 5.2.3 Synthesis of Urea Derivatives 174 5.2.4 Synthesis of Quinazolines 175 5.3 CO2 Conversion with C─O Bond Formation 178 5.3.1 Synthesis of Cyclic Carbonates 178 5.3.1.1 Cyclic Carbonate Synthesis from Epoxide and CO2 178 5.3.1.2 α‐Alkylidene Cyclic Carbonate Synthesis from Carboxylative Cyclization of Propargyl Alcohols with CO2 181 5.3.1.3 Cyclic Carbonate Synthesis from Carboxylative Cyclization of 1,2‐Diols with CO2 182 5.3.1.4 One‐Pot Stepwise Synthesis of Cyclic Carbonates Directly from Olefins or Vicinal Halohydrins with CO2 183 5.3.2 Synthesis of Linear Carbonates 185 5.4 CO2 Conversion with C─S Bond Formation 187 5.4.1 Synthesis of Dithioacetals 187 5.4.2 Synthesis of Benzothiazolones 188 5.4.3 Synthesis of Benzothiazoles 189 5.5 Carbon–Heteroatom Bond Formation from the Captured CO2 or CO2 Derivatives 190 5.6 Conclusions 191 Abbreviations 192 References 193 6 Carbonyl‐Ene Reactions of Alkenes with Carbon Dioxide 199 Yasuyuki Mori and Masanari Kimura 6.1 Introduction 199 6.2 Carbonyl‐Ene Reactions of Alkenes with CO2 199 6.2.1 Organoaluminum and Pyridine Derivative‐Mediated Coupling Reaction 199 6.2.2 Light‐Induced Copper‐Catalyzed Carboxylation of Allylic C─H Bonds 204 6.2.3 Copper and Aluminum Ate Compound System for Carboxylation of Allylic C─H Bond of Alkenes 208 6.2.4 Cobalt‐Catalyzed Carboxylation of Allylic C─H Bond of Terminal Alkenes 212 6.2.5 Nickel‐Catalyzed Carbonyl‐ene‐Type Reaction of Terminal Alkenes with CO2 217 References 223 7 Recent Advances in Electrochemical Carboxylation of Organic Compounds for CO2 Valorization 225 Luca Dell’Amico, Marcella Bonchio, and Xavier Companyo 7.1 Introduction 225 7.2 Electrochemical Carboxylation of Unsaturated Compounds 228 7.3 Electrochemical Carboxylation of Organic Halides 236 7.4 Stereoselective Electrochemical Carboxylations 245 7.5 Conclusions 249 References 250 8 Photocatalysis as a Powerful Tool for the Utilization of CO2 in Organic Synthesis 253 Daniel Riemer and Shoubhik Das 8.1 Key Intermediate Involving Substrate with Late‐Stage CO2 Addition/Insertion 254 8.1.1 Unsaturated Substrates 254 8.1.2 Aryl Halides 264 8.1.3 Benzylic C─H Bonds 267 8.2 CO2 Substrate Adduct as the Key Intermediate 269 8.3 CO2 Radical Anion as a Key Intermediate 276 8.4 Hydroxycarbonyl Radical as a Key Intermediate 282 8.5 Conclusion and Outlook 284 References 285 9 Direct Carboxylation of Alkenes and Alkynes 291 Martin Pichette Drapeau, Johannes Schranck, and Anis Tlili 9.1 Introduction 291 9.2 Carboxylation of Alkenes 291 9.2.1 Stoichiometric Carboxylation of Alkenes 291 9.2.2 Catalytic Hydrocarboxylation of Alkenes 295 9.2.3 Photoinduced Hydrocarboxylation of Alkenes 300 9.2.4 Difunctionalization of Alkenes with Carbon Dioxide 304 9.3 Carboxylation of Alkynes 305 9.3.1 Carboxylation of Terminal Alkynes 305 9.3.1.1 Synthesis of Propiolic Esters 305 9.3.1.2 Synthesis of Propiolic Acids 308 9.3.2 Synthesis of Acrylic Acid Derivatives 316 9.3.2.1 Hydrocarboxylation 316 9.3.2.2 Alkyl‐ and Arylcarboxylations 321 9.3.2.3 Sila‐ and Boracarboxylations 323 9.3.3 Carboxylation Leading to Cyclization Products 324 9.4 Conclusions 326 References 327 10 Homogeneous Iron Catalysts for the Synthesis of Useful Molecules from CO2 331 Francesco Della Monica and Carmine Capacchione 10.1 Introduction 331 10.2 Reductive Processes 332 10.2.1 Hydrogenation 332 10.2.2 Hydrosilylation and Hydroboration 335 10.2.3 Mechanistic Details 336 10.3 Nonreductive Processes 337 10.3.1 Cyclic Organic Carbonates and Aliphatic Polycarbonates from CO2 and Epoxides 337 10.3.2 Mechanistic Details 346 10.3.3 Stereochemistry of Cyclic Organic Carbonates 354 10.3.4 Oxazolidinones 358 10.4 Conclusions 360 References 360 11 NHC‐catalyzed CO2 Fixations in Organic Synthesis 367 Vishakha Goyal, Naina Sarki, Anand Narani, and Kishore Natte 11.1 Introduction 367 11.2 Direct C–H Activation with CO2 369 11.2.1 C–H Activation of Terminal Alkynes 369 11.2.2 Carboxylation of Arenes and Heteroarenes 373 11.2.3 Carboxylation of Alkenes and Organoboronic Esters 376 11.3 Oxidation of Aldehydes with CO2 376 11.4 Cyclization Reactions with CO2 379 11.4.1 Synthesis of Cyclic Carbonates from CO2 and Epoxides 379 11.4.2 Cyclization of CO2 in Presence of NHC–CO2 Adducts 380 11.4.3 Cyclization of CO2 in Presence of Metal NHCs Complexes 382 11.4.4 Cyclization of Propargylic Amines 385 11.5 Alkylation with CO2 387 11.5.1 N‐methylation 387 11.5.2 N‐formylation 388 11.6 Miscellaneous 390 11.7 Summary 393 References 393 12 Silver‐Catalyzed CO2 Fixation 397 Kodai Saito and Tohru Yamada 12.1 Introduction 397 12.2 Historical Background of Carbon Dioxide Fixation into Organosilver Complexes 398 12.3 Carboxylation of Terminal Alkynes 399 12.4 Cascade Carboxylative Cyclization 404 12.5 Silver‐Catalyzed Sequential Carboxylative Cyclization of Propargyl Alcohols 405 12.6 Synthesis of Cyclic Carbonate 405 12.7 Catalytic Asymmetric Synthesis of Cyclic Carbonate 411 12.8 Three‐Component Reaction of Propargyl Alcohols, Carbon Dioxide, and Nucleophiles 411 12.9 CO2‐Mediated Transformation of Propargyl Alcohols 412 12.10 Transformation of Amine Derivatives 417 12.11 Cascade Carboxylation and Cyclization of Unsaturated Amine Derivatives 417 12.11.1 Benzoxazine‐2‐one from o‐Alkynylaniline and Carbon Dioxide 418 12.11.2 Cascade Carboxylation – Addition to Allenes 418 12.11.3 Three‐Component Reaction of Carbon Dioxide, Amines, and Aryloxyallens 419 12.12 Domino Carboxylation – Cyclization – Migration of Unsaturated Amines 421 12.12.1 Carboxylation Involving C-C Bond Formation – Sequential Cyclization 423 12.12.2 Carboxylation of Enolate – Sequential Cyclization 423 12.12.3 Carbon Dioxide Incorporation Reaction Using Other Carbanions 427 12.13 Carboxylation of Arylboronic Esters 428 12.13.1 Functionalization of Terminal Epoxides 431 12.14 Conclusion 432 References 433 Index 437

About the Author :
Dr. Shoubhik Das in an independant group leader at the Georg-August-University of Goettingen, Germany since 2015. He has studied in India and finished his MSc from IIT Kharagpur in 2006. Subsequently, he moved to UK to join GlaxoSmithKline. In 2008, he started his PhD under the supervision of Prof. Matthias Beller at Leibniz Institut für Katalyse, Germany. In 2011, he finished his PhD and joined the research group of Prof. Matthew J. Gaunt as a post-doctoral research associate at University of Cambridge. In 2013, Dr. Das moved to EPFL, Switzerland and joined the group of Prof. Paul J. Dyson as a scientist.