Chemical Transformations of C1 Compounds

Xiao-Feng Wu, PhD, has published over 400 publications in international journals and is the editor or author of 10 books. He received his doctorate from the Leibniz Institute for Catalysis in Germany. Buxing Han, PhD, is Professor and Academician at the Institute of Chemistry, Chinese Academy of Sciences. He has published more than 300 papers and authored over 20 patents. He received his doctorate from the Chinese Academy of Sciences in 1988. Kuiling Ding, PhD, is Executive Vice President at Shanghai Jiaotong University. He received his doctorate in 1990 from Nanjing University and is a member of the Chinese Academy of Sciences. Zhongmin Liu, PhD, is Director of the Dalian Institute of Chemical Physics and the Qingdao Institute of Bioenergy and Bioprocess Technology. He received his doctorate in Physical Chemistry from the Dalian Institute of Chemical Physics in 1990.

• Volume 11 Direct Conversions of Methane via Homogeneous Processes 1Hui Chen, Anhua Hu, Liang Chang, Qing An, Hui Pan, and Zhiwei Zuo1.1 Introduction 11.2 Formation of Methanol and Its Derivatives 21.2.1 Electrophilic Activation 21.2.2 Radical-Mediated Activation 91.3 Formation of Acetic Acid 111.3.1 K2S2O8 Oxidant-Based Systems 121.3.2 O2 Oxidant-Based Systems 141.3.3 H2SO4 Oxidant-Based Systems 151.3.4 Other Oxidant-Based Systems 171.4 Formation of Methanesulfonic Acid 171.5 Formation of Borylated Products 191.6 Formation of Aminated Products 211.7 Formation of Alkylated Products 231.8 Summary and Conclusions 24References 262 Chemical Transformations of Methanol 31Zhengkai Chen and Xiao-Feng Wu2.1 Introduction 312.2 Methylation 312.2.1 C-Methylation 322.3 N-Methylation 422.4 Hydroxymethylation 492.5 N-Formylation 512.6 Methoxylation 542.7 The Reactions Using Methanol as the C1 Source 622.8 Conclusions 65References 653 Synthesis of Olefins from CH3OH 71Wenna Zhang, Yingxu Wei, and Zhongmin Liu3.1 Introduction 713.2 Catalysts of Methanol to Olefins 733.2.1 ZSM-5 Catalyst with MFI Topology Structure 733.2.2 SAPO-34 with CHA Topology Structure 733.2.3 Other Catalysts with 8-MR Pore Opening and Cavity Structure 763.3 Catalytic Reaction Mechanism of Methanol Conversion 773.3.1 Reaction Course of MTO Process 773.3.2 Direct Mechanism of Methanol Conversion 783.3.2.1 Carbonylation-Based Mechanism 793.3.2.2 Methoxymethyl Carbocation Mechanism 813.3.2.3 Methane-formaldehyde Mechanism 813.3.2.4 Extra-Framework Aluminum-Assisted (EFAL) Initial C—C Bond Formation 833.3.2.5 Oxonium Ion-ylide Mechanism 853.3.2.6 SMS/TMO-mediated DME/Methanol Activation Mechanism 883.3.3 Autocatalysis Character of Methanol Conversion 883.3.4 Indirect Mechanism of Methanol Conversion 903.3.4.1 Hydrocarbon Pool Mechanism 913.3.4.2 Dual-cycle Mechanism 973.3.4.3 Cyclopentadienes-Based Cycle 1003.3.5 Evolution from Direct Mechanism to Indirect Mechanism 1023.3.6 Reaction Network of MTO Process 1053.4 Deactivation of MTO Reaction 1073.4.1 Low-temperature Deactivation Mechanism of SAPO-34 in MTO Reaction 1083.4.2 High-temperature Deactivation Mechanism of SAPO-34 in MTO Reaction 1093.4.3 A Cage-passing Growth Deactivating Model on SAPO-34 1123.5 DMTO Process Developments 1153.5.1 Scale-up Synthesis of DMTO Catalyst 1153.5.2 Industrial Test of DMTO Technology 1153.5.3 DMTO Technology Commercialization 1173.5.4 DMTO-II Technology 1173.5.5 DMTO-III Technology 1183.6 Conclusions and Outlook 119Acknowledgments 119References 1194 Carbonylation of Methanol: A Versatile Reaction 127Dipak K. Dutta4.1 Introduction 1274.2 Carbonylation of Methanol to Produce Acetic Acid 1314.2.1 Industrial Processes 1314.2.1.1 The Cobalt-Based BASF Process 1314.2.1.2 Rhodium-Catalyst-Based Monsanto Carbonylation Process 1324.2.1.3 The Iridium-Based Cativa Process of BP Chemicals 1354.2.2 Laboratory Processes 1374.2.2.1 Homogeneous Catalysts 1374.3 Conclusion and Future Aspects 151Acknowledgments 152References 1525 Formaldehyde as C1 Synthon in Organic Synthesis 157Wanfang Li and Xiao-Feng Wu5.1 Introduction 1575.2 Formaldehyde as Methylenes (–CH2–) 1595.2.1 Methylenes Linking Two Aryl Groups 1595.2.2 Methylenes Linking Two Alkyl Groups 1655.2.3 Methylenes Linking Carbon and Nitrogen 1675.2.3.1 Mannich-Type Reactions 1675.2.3.2 Formation of Propargyl Amines 1675.2.3.3 Synthesis of Allyl and Benzyl Amines 1725.2.4 Methylenes Linking Carbon and Oxygen 1765.2.4.1 Oxa-Pictet–Spengler Reaction 1765.2.4.2 Formation of Propargyl Alcohols 1785.2.5 Methylenes Linking Carbon and Halogens 1795.2.6 Methenynation Reactions (=CH2) 1805.2.6.1 Formation of Terminal Allenes 1805.2.6.2 Methenynation of Allylic and Benzylic Positions 1825.2.6.3 Methylenynation of Carbonyls via Wittig Reaction 1835.2.6.4 α-Methylenynations of Carbonyls 1845.2.7 Methylenen Linking Two Heteroatoms 1855.3 Hydroxymethylation Reagent (–CH2OH) 1925.3.1 Hydroxymethylation of Carbonyl Substrates 1925.3.2 Prins and Carbonyl-Ene Reactions with Formaldehyde 1995.3.3 Morita–Baylis–Hillman Reaction with Formaldehyde 2055.3.4 Reductive Hydroxymethylation of Alkenes and Alkynes Allenes 2065.3.5 Hydromethoxylation of Organometallics 2115.3.6 Hydromethylation of Miscellaneous Compounds 2135.4 As CO Source 2175.4.1 Carbonylation Reactions 2175.4.1.1 Carbonylation of Aryl Halides 2175.4.1.2 Carbonylation of Alkenes and Alkynes 2205.4.2 Hydroformylations Reactions 2235.4.3 Formaldehyde for Ketone Synthesis 2275.5 As Hydrogen Donor and Accepter 2275.6 As Methylation and Formylation Reagents 2305.6.1 Methylation Reagent 2305.6.2 Formylation Reagent 2325.7 Formaldehyde as Ligand and Reductant in Organometallic Chemistry 2345.8 Summary and Outlook 235References 2366 Organic Transformations of HCO2H 249Zhiping Yin and Xiao-Feng Wu6.1 Introduction 2496.2 Providing Carbonyl Moiety 2496.2.1 Reactions with Aryl Halides or Triflates 2506.2.2 Reactions with Alkenes or Alkynes 2546.2.3 Reactions with Amines 2566.3 Providing Carboxyl Moiety 2576.3.1 Reactions with Aryl Halides 2576.3.2 Reactions with Arenes 2586.3.3 Reactions with Alkenes or Alkynes 2606.4 As Hydrogen Source 2636.4.1 Reducing Alkenes or Alkynes 2636.4.2 Reducing Carbonyl Groups 2686.4.3 Hydrogenolysis Benzylic C—O Bonds 2726.4.4 Reducing Nitro Groups 2756.4.5 Reducing Unsaturated C—N Bonds 2786.5 Other Reactions 2816.6 Conclusion 283References 2837 The Multifunctional Materials for Heterogenous Carboxylation: From Fundamental Understanding to Industrial Applications 289Yunjie Ding, Li Yan, and Xiangen Song7.1 Introduction 2897.2 Hydroformylation of Olefins 2897.2.1 Heterogeneous Hydroformylation 2907.2.1.1 Hydroformylation of Ethylene 2907.2.1.2 Hydroformylation of Propene 2927.2.1.3 Hydroformylation of Butenes 2937.2.1.4 Hydroformylation of Long-Chain Olefins 2987.2.1.5 Asymmetric Hydroformylation 3017.3 Heterogeneous Carbonylation 3037.4 Other Catalytic Reactions 3077.4.1 Asymmetric Hydrogenation 3077.4.2 Alkoxycarbonylation 3087.4.3 Suzuki–Miyaura Coupling Reactions 3117.4.4 Oxidative Heck Reaction 3127.4.5 Hydrogenation 3137.4.6 Chemoselective Decarbonylation of Aldehydes 3157.4.7 Cyclic Addition Reaction of CO2 and Epoxides 3157.5 Summary and Perspective 319Acknowledgments 319Conflict of Interest 319References 3198 Recent Hydrocarbonylation of Unsaturated Hydrocarbons with Homogeneous Catalyst 325Kaiwu Dong and Kuiling Ding8.1 Introduction 3258.2 Transition Metal-Catalyzed Hydroformylation 3278.2.1 Cobalt-Catalyzed Hydroformylation 3288.2.2 Rhodium-Catalyzed Hydroformylation 3328.2.3 Ruthenium-Catalyzed Hydroformylation 3528.2.4 Iron-, Osmium-, and Iridium-Catalyzed Hydroformylation 3578.2.5 Metal-Free Hydroformylation 3608.3 Transition Metal-Catalyzed Hydrocarbonylation (Reppe Carbonylation) 3618.3.1 Palladium-Catalyzed Hydrocarbonylation 3618.3.1.1 Palladium-Catalyzed Hydrocarbonylation of Alkenes 3618.3.1.2 Palladium-Catalyzed Enantioselective Hydrocarbonylation of Alkenes 3838.3.1.3 Palladium-Catalyzed Hydrocarbonylation of Alkynes 3868.3.1.4 Palladium-Catalyzed Hydrocarbonylation of In Situ Generated Alkenes 3938.3.2 Nickel-Catalyzed Hydrocarbonylation 3958.3.3 Ruthenium- and Platinum-Catalyzed Hydrocarbonylation 397Acknowledgments 399List of Abbreviations 399References 4009 Carbonylation of C(sp2)—X Bonds 415Huaanzi Hu, Jian Liu, and Qiang Zhu9.1 Introduction 4159.2 Common Aspects 4159.2.1 Types of C(sp2)—X 4169.2.1.1 Aryl/Vinyl Halides 4169.2.1.2 Aryl/Vinyl Pseudohalides 4179.2.2 Catalysts or Initiators 4189.2.2.1 Noble Metal Catalysts 4189.2.2.2 Non-Noble Metal Catalysts 4209.2.2.3 Photoinitiated Radical Process 4219.2.2.4 Other Radical Process 4259.2.3 CO Sources 4259.2.3.1 Metal Carbonyl Complex 4269.2.3.2 Formic Acid and Its Derivatives 4269.2.3.3 Others 4289.2.3.4 The Two-Chamber System 4319.2.4 Nucleophiles 4319.3 Domino Carbonylations 4349.3.1 Intramolecular Domino Carbonylations 4349.3.2 Intermolecular Domino Carbonylations 4369.4 Double Carbonylations 4389.4.1 Adjacent Carbonyl Groups 4399.4.2 Nonadjacent Carbonyl Groups 4419.5 Asymmetric Carbonylations 4429.6 Applications 4459.6.1 Synthesis of Heterocycles 4459.6.2 Drugs or Natural Products 448References 45210 Carbonylation of C(sp3)—X Bonds Utilizing CO 459Renyi Shi and Aiwen Lei10.1 Introduction 45910.2 Carbonylation of Allyl Compounds 46010.2.1 Allyl Metallic Reagents 46010.2.2 Allyl Halides 46410.2.3 Allyl Esters 46610.2.4 Allyl Ethers 47210.2.5 Allyl Alcohols 47310.2.6 Allyl Amines 47710.3 Carbonylation of Benzylic Compounds 47710.3.1 Benzyl Halides 47710.3.2 Benzyl Alcohol 48710.3.3 Benzyl Amines 49010.3.4 Benzyl-H 49110.3.5 Others 49210.4 α-Carbonylation of Carbonyl Derivatives 49310.4.1 α-Halide Carbonyl Derivatives 49310.4.2 α-H Carbonyl Derivatives 49410.4.3 Other 49410.5 Carbonylation of Aliphatic Alkyl Compounds 49510.5.1 Alkyl Metallic Reagents 49510.5.2 Aliphatic Alkyl Halides 49610.5.3 Carbonylation of Heterocycles 50310.5.4 Aliphatic C—H Bonds 51010.6 Conclusion 515References 516Volume 211 Carbonylative C—H Bond Activation 533Angela Kaiser and Bruce A. Arndtsen12 Recent Advances in Radical Carbonylation 567Shuhei Sumino, Takahide Fukuyama, and Ilhyong Ryu13 Asymmetric Carbonylation Reactions 611Shao-Tao Bai, Jialin Wen, and Xumu Zhang14 Carbonylative Synthesis of DPC (Diphenyl Carbonate) 667Raffaella Mancuso and Bartolo Gabriele15 Oxidative Carbonylation of Amines 687Yanwei Cao, Lin He, and Chungu Xia16 Carbonylation of Nitroarenes and Related Compounds 721Fabio Ragaini and Francesco Ferretti17 Zeolite-Catalyzed Carbonylation of Dimethyl Ether 763Ensheng Zhan, Zhiping Xiong, and Wenjie Shen18 Complex Natural Product Total Syntheses Facilitated by Palladium-Catalyzed Carbonylative Cyclizations 793Yiyang Luo, Lei Li, and Mingji Dai19 Metal-Catalyzed Alternating Polymerization Reactions with Carbon Monoxide 827Werner Oberhauser20 CO Hydrogenation 861Jingting Hu, Wei Zhou, Kang Cheng, Qinghong Zhang, and Ye Wang21 Carboxylation with Carbon Dioxide as a C1 Source via Carbon–Carbon Bond Forming Reactions 909Tetsuaki Fujihara22 Cyclization Reactions with CO2 973Arjan W. Kleij23 Reduction of CO2 to Formic Acid 1003Bernard B. A. Bediako, Qingli Qian, and Buxing Han24 Reduction of CO2 to CO and Their Applications 1027Karoline T. Neumann, Anne K. Ravn, Martin B. Johansen, Aske S. Donslund, Magnus H. Rønne, Haraldur G. Gudmundsson, and Troels SkrydstrupVolume 325 Hydrogenation of CO2 to Chemicals with Green Hydrogen 1073Feng Sha, Xinyi Liu, Shan Tang, Jijie Wang, and Can Li26 Methylation Reactions with CO2 1185Xiang-Yang Yao, Zhi-Wen Yang, Hong-Ru Li, and Liang-Nian He27 Using CO2 as –CH– and –CH2– Sources 1217Xiao-Wang Chen, Yong-Yuan Gui, Yuan-Xu Jiang, Ke Jing, Ya-Nan Niu, Yue-Ming Jiang, and Da-Gang Yu28 Catalytic Asymmetric Transformation of CO2 1265Fachao Yan, Jian-Fei Bai, and Yuehui Li29 Polymerization Reactions with CO2 1305Wen-Bing Li and Xiao-Bing Lu30 Transition-Metal-Catalyzed C–CN Cross-Coupling 1337Murugan Dhanalakshmi and Pazhamalai Anbarasan31 Recent Advancement in Transition-Metal-Catalyzed Hydrocyanation of Nonpolar Unsaturated Compounds 1367Rongrong Yu, Kaiwu Dong, and Xianjie Fang32 Organic Transformations with MeNO2 1397Debarati Das, Nilam Patil, and Bhalchandra M. Bhanage33 Applications of DMF as a Reagent in Organic Synthesis 1439Zechao Wang and Xiao-Feng Wu34 Advances in the Synthesis of Methylated Products Through Direct Approaches: A Guide for Selecting Methylation Reagents 1475Yantao Chen35 Organic Transformations with DCM, CCl4, CHCl3, and CHBr3 and Other Related Reactions 1577Yunyun Liu and Jie-Ping Wan36 Trifluoromethylation with CF3I and Other Related Reagents 1609Xiu-Hua Xu and Feng-Ling Qing37 The Applications of Dimethyl Sulfoxide as a One-Carbon Source in Organic Synthesis 1647Chong-Liang Li and Xiao-Feng WuIndex 1667