CO2 as a Building Block in Organic Synthesis

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.

• 1 Photochemical and Substrate‐Driven CO2 Conversion 1Bart Limburg, Cristina Maquilon, and Arjan W. Kleij1.1 Introduction 11.2 Iodine Activation of (Homo)Allylic Substrates 31.3 Substrate Activation Via Radical Addition/Photochemical Oxidation Processes 91.4 Substrate‐Induced Activation of Oxiranes 121.5 Substrate‐Involved Activation of Oxetanes and Azetidines 211.6 Concluding Remarks 21References 222 C–H Carboxylations with CO2 29Uttam Dhawa, Isaac Choi, and Lutz Ackermann2.1 Introduction 292.2 Transition‐Metal‐Catalyzed C–H Carboxylation 302.2.1 Copper‐Catalyzed C–H Carboxylation 302.2.2 Cobalt‐Catalyzed C–H Carboxylation 362.2.3 Nickel‐Catalyzed C–H Carboxylation 362.2.4 Molybdenum‐Catalyzed C–H Carboxylation 382.2.5 Ruthenium‐Catalyzed C–H Carboxylation 382.2.6 Rhodium‐Catalyzed C–H Carboxylation 392.2.7 Palladium‐Catalyzed C–H Carboxylation 412.2.8 Silver‐Catalyzed C–H Carboxylation 422.2.9 Iridium‐Catalyzed C–H Carboxylation 452.2.10 Gold‐Catalyzed C–H Carboxylation 452.2.11 Neodymium‐Catalyzed C–H Carboxylation 452.3 Metal‐Free C–H Carboxylation 462.3.1 Base‐Mediated C–H Carboxylation 462.3.2 Electro‐Catalyzed C–H Carboxylation 492.3.3 Lewis Acid‐Mediated Carboxylation 492.3.4 Light‐Driven Carboxylation 502.4 CO2 Carboxylation Promoted by Transition Metal Complexes 522.5 Conclusions 53References 533 Transition‐Metal‐Catalyzed C–H Carboxylation 59Joaquim Caner and Nobuharu Iwasawa3.1 Introduction 593.2 Direct C–H Carboxylation of Electron‐Deficient Arenes and (Hetero) Arenes Catalyzed by Basic Complexes 593.3 Direct Carboxylation of Inert Csp2─H Bonds 663.3.1 Rhodium‐Catalyzed C–H Carboxylation Reactions 663.3.2 Palladium‐Catalyzed C–H Carboxylation Reactions 763.4 Direct Carboxylation of Csp3─H Bonds 853.5 Summary and Outlook 89References 904 Fixation of CO2 in Organic Molecules with Heterogeneous Catalysts 95Dongcheng He, Hongli Wang, and Feng Shi4.1 Introduction 954.2 CO2 Cycloaddition to Epoxide 964.2.1 Oxides 964.2.2 Zeolite Catalysts 974.2.3 Supported Nanoparticle and Lewis Acid Catalysts 984.2.4 Carbon and Its Derivatives 994.2.5 Salen, Porphyrin, and Phthalocyanine Catalyst 1014.2.6 Ionic Liquid Catalyst 1034.2.7 Metal−Organic Framework (MOF) Catalyst 1084.2.8 Bifunctional Catalyst 1124.2.9 Other Catalysts 1204.3 Reactions of Aziridines and CO2 1204.4 Reactions of Polyalcohols/Olefins and CO2 1214.5 Reaction of Propargyl Alcohols/Propargyl Amines and CO2 1244.6 Reactions of Terminal Alkynes and CO2 1254.7 Formylation of Amines and CO2 1274.8 Methylation of Amines and CO2 1304.9 Other Reactions of Amines and CO21314.10 Hydroformylation of CO2 and Olefins into Alcohols 1334.11 Reactions of Aromatic Halides and CO2 1344.12 Reactions of 2‐Aminobenzonitriles and CO2 1364.13 Conclusions 137References 1385 CO2 Fixation into Organic Molecules via Carbon–Heteroatom Bond Formation 155Yu‐Nong Li, Hong‐Ru Li and Liang‐Nian He5.1 Introduction 1555.2 CO2 Conversion with C─N Bond Formation 1575.2.1 Synthesis of Oxazolidinones 1575.2.1.1 Oxazolidinone Synthesis from Aziridine and CO2 1585.2.1.2 Oxazolidinone Synthesis from Olefin, a Nitrogen Source, and CO2 1635.2.1.3 Oxazolidinone Synthesis from Amino Alcohols and CO2 1645.2.1.4 Oxazolidinone Synthesis from Carboxylative Cyclization of Propargyl Amines with CO2 1655.2.1.5 Oxazolidinone Synthesis from Propargyl Alcohol, Aliphatic Amines/2‐Aminoethanols, and CO2 1675.2.1.6 Photoinduced Radical‐Initiated Carboxylative Cyclization of Allyl Amines with CO2 1705.2.2 Synthesis of Isocyanates and Linear Carbamates 1725.2.3 Synthesis of Urea Derivatives 1745.2.4 Synthesis of Quinazolines 1755.3 CO2 Conversion with C─O Bond Formation 1785.3.1 Synthesis of Cyclic Carbonates 1785.3.1.1 Cyclic Carbonate Synthesis from Epoxide and CO2 1785.3.1.2 α‐Alkylidene Cyclic Carbonate Synthesis from Carboxylative Cyclization of Propargyl Alcohols with CO2 1815.3.1.3 Cyclic Carbonate Synthesis from Carboxylative Cyclization of 1,2‐Diols with CO2 1825.3.1.4 One‐Pot Stepwise Synthesis of Cyclic Carbonates Directly from Olefins or Vicinal Halohydrins with CO2 1835.3.2 Synthesis of Linear Carbonates 1855.4 CO2 Conversion with C─S Bond Formation 1875.4.1 Synthesis of Dithioacetals 1875.4.2 Synthesis of Benzothiazolones 1885.4.3 Synthesis of Benzothiazoles 1895.5 Carbon–Heteroatom Bond Formation from the Captured CO2 or CO2 Derivatives 1905.6 Conclusions 191Abbreviations 192References 1936 Carbonyl‐Ene Reactions of Alkenes with Carbon Dioxide 199Yasuyuki Mori and Masanari Kimura6.1 Introduction 1996.2 Carbonyl‐Ene Reactions of Alkenes with CO2 1996.2.1 Organoaluminum and Pyridine Derivative‐Mediated Coupling Reaction 1996.2.2 Light‐Induced Copper‐Catalyzed Carboxylation of Allylic C─H Bonds 2046.2.3 Copper and Aluminum Ate Compound System for Carboxylation of Allylic C─H Bond of Alkenes 2086.2.4 Cobalt‐Catalyzed Carboxylation of Allylic C─H Bond of Terminal Alkenes 2126.2.5 Nickel‐Catalyzed Carbonyl‐ene‐Type Reaction of Terminal Alkenes with CO2 217References 2237 Recent Advances in Electrochemical Carboxylation of Organic Compounds for CO2 Valorization 225Luca Dell’Amico, Marcella Bonchio, and Xavier Companyo7.1 Introduction 2257.2 Electrochemical Carboxylation of Unsaturated Compounds 2287.3 Electrochemical Carboxylation of Organic Halides 2367.4 Stereoselective Electrochemical Carboxylations 2457.5 Conclusions 249References 2508 Photocatalysis as a Powerful Tool for the Utilization of CO2 in Organic Synthesis 253Daniel Riemer and Shoubhik Das8.1 Key Intermediate Involving Substrate with Late‐Stage CO2 Addition/Insertion 2548.1.1 Unsaturated Substrates 2548.1.2 Aryl Halides 2648.1.3 Benzylic C─H Bonds 2678.2 CO2 Substrate Adduct as the Key Intermediate 2698.3 CO2 Radical Anion as a Key Intermediate 2768.4 Hydroxycarbonyl Radical as a Key Intermediate 2828.5 Conclusion and Outlook 284References 2859 Direct Carboxylation of Alkenes and Alkynes 291Martin Pichette Drapeau, Johannes Schranck, and Anis Tlili9.1 Introduction 2919.2 Carboxylation of Alkenes 2919.2.1 Stoichiometric Carboxylation of Alkenes 2919.2.2 Catalytic Hydrocarboxylation of Alkenes 2959.2.3 Photoinduced Hydrocarboxylation of Alkenes 3009.2.4 Difunctionalization of Alkenes with Carbon Dioxide 3049.3 Carboxylation of Alkynes 3059.3.1 Carboxylation of Terminal Alkynes 3059.3.1.1 Synthesis of Propiolic Esters 3059.3.1.2 Synthesis of Propiolic Acids 3089.3.2 Synthesis of Acrylic Acid Derivatives 3169.3.2.1 Hydrocarboxylation 3169.3.2.2 Alkyl‐ and Arylcarboxylations 3219.3.2.3 Sila‐ and Boracarboxylations 3239.3.3 Carboxylation Leading to Cyclization Products 3249.4 Conclusions 326References 32710 Homogeneous Iron Catalysts for the Synthesis of Useful Molecules from CO2 331Francesco Della Monica and Carmine Capacchione10.1 Introduction 33110.2 Reductive Processes 33210.2.1 Hydrogenation 33210.2.2 Hydrosilylation and Hydroboration 33510.2.3 Mechanistic Details 33610.3 Nonreductive Processes 33710.3.1 Cyclic Organic Carbonates and Aliphatic Polycarbonates from CO2 and Epoxides 33710.3.2 Mechanistic Details 34610.3.3 Stereochemistry of Cyclic Organic Carbonates 35410.3.4 Oxazolidinones 35810.4 Conclusions 360References 36011 NHC‐catalyzed CO2 Fixations in Organic Synthesis 367Vishakha Goyal, Naina Sarki, Anand Narani, and Kishore Natte11.1 Introduction 36711.2 Direct C–H Activation with CO2 36911.2.1 C–H Activation of Terminal Alkynes 36911.2.2 Carboxylation of Arenes and Heteroarenes 37311.2.3 Carboxylation of Alkenes and Organoboronic Esters 37611.3 Oxidation of Aldehydes with CO2 37611.4 Cyclization Reactions with CO2 37911.4.1 Synthesis of Cyclic Carbonates from CO2 and Epoxides 37911.4.2 Cyclization of CO2 in Presence of NHC–CO2 Adducts 38011.4.3 Cyclization of CO2 in Presence of Metal NHCs Complexes 38211.4.4 Cyclization of Propargylic Amines 38511.5 Alkylation with CO2 38711.5.1 N‐methylation 38711.5.2 N‐formylation 38811.6 Miscellaneous 39011.7 Summary 393References 39312 Silver‐Catalyzed CO2 Fixation 397Kodai Saito and Tohru Yamada12.1 Introduction 39712.2 Historical Background of Carbon Dioxide Fixation into Organosilver Complexes 39812.3 Carboxylation of Terminal Alkynes 39912.4 Cascade Carboxylative Cyclization 40412.5 Silver‐Catalyzed Sequential Carboxylative Cyclization of Propargyl Alcohols 40512.6 Synthesis of Cyclic Carbonate 40512.7 Catalytic Asymmetric Synthesis of Cyclic Carbonate 41112.8 Three‐Component Reaction of Propargyl Alcohols, Carbon Dioxide, and Nucleophiles 41112.9 CO2‐Mediated Transformation of Propargyl Alcohols 41212.10 Transformation of Amine Derivatives 41712.11 Cascade Carboxylation and Cyclization of Unsaturated Amine Derivatives 41712.11.1 Benzoxazine‐2‐one from o‐Alkynylaniline and Carbon Dioxide 41812.11.2 Cascade Carboxylation – Addition to Allenes 41812.11.3 Three‐Component Reaction of Carbon Dioxide, Amines, and Aryloxyallens 41912.12 Domino Carboxylation – Cyclization – Migration of Unsaturated Amines 42112.12.1 Carboxylation Involving C-C Bond Formation – Sequential Cyclization 42312.12.2 Carboxylation of Enolate – Sequential Cyclization 42312.12.3 Carbon Dioxide Incorporation Reaction Using Other Carbanions 42712.13 Carboxylation of Arylboronic Esters 42812.13.1 Functionalization of Terminal Epoxides 43112.14 Conclusion 432References 433Index 437