Green Solvents in Organic Synthesis

Xiao-Feng Wu, PhD, is a Professor at Dalian Institute of Chemical Physics, CAS.Zhiping Yin, PhD, is a Professor at the School of Pharmacy of Jiangsu University.Liang-Nian He, PhD, is a Professor at Nankai University.Feng Wang, PhD, serves as the vice director of Dalian Institute of Chemical Physics, CAS and the director of the Biomass-Conversion and Bio-Energy division at the Bioenergy Chemical Group.

• 1 Recent Achievements in Organic Reactions in Alcohols 1Lan Zhao, Man Zhao, Meng-Ge Wei, Hong-Ru Li, and Liang-Nian He1.1 Introduction 11.2 Alcohols as Green Solvents 61.2.1 Hydrogenation/Reduction Reaction 61.2.2 Oxidation Reaction 81.2.3 Substitution Reaction 101.2.4 Addition Reaction 111.2.5 Cyclization Reaction 131.2.6 Coupling Reaction 181.2.7 Condensation/Ring Condensation Reaction 211.3 Alcohols as Green Solvents and Catalysts 281.3.1 Addition Reaction 281.3.2 Cyclization Reaction 281.3.3 Coupling Reaction 301.3.4 Condensation Reaction 301.3.5 Metathesis Reaction 351.4 Alcohols as Green Solvents and Hydrogen Donors 351.5 Miscellaneous 391.5.1 Polyethylene Glycol as a Solvent for CO 2 Capture and Conversion 391.5.2 Polyethylene Glycol Radical-Initiated Oxidation Reactions in Compressed Carbon Dioxide 411.5.3 Ring-Opening Reaction 431.6 Summary and Concluding Remarks 45Acknowledgments 46References 462 Recent Achievements in Organic Reactions in MeCN 51Tongtong Xing, Guizhi Zhai, Linna Wu, Xiaofen Wang, and Zechao Wang2.1 Introduction 512.2 MeCN in Transition Metal-catalyzed Reactions Without Radicals Involved 522.2.1 Transition Metal-catalyzed Addition Reactions in MeCN 522.2.2 Transition Metal-catalyzed Oxidation Reactions in MeCN 562.2.3 Transition Metal-catalyzed Reduction Reactions in MeCN 642.2.4 Transition Metal-catalyzed Substitution Reactions in MeCN 662.2.5 Transition Metal-catalyzed Cyclization Reactions in MeCN 742.3 MeCN in Transition Metal-free Catalyzed Reactions Without Radicals Involved 802.3.1 Transition Metal-free Catalyzed Cyclization Reactions in MeCN 802.3.2 Transition Metal-free Catalyzed Multicomponent Reactions in MeCN 842.3.3 Transition Metal-free Catalyzed C—X Bond Formation in MeCN 872.4 MeCN in C—X Bonds Formation With Radicals Involved 902.4.1 C—C, C—Si Bond Formation in MeCN 902.4.2 C—N, C—P Bond Formation in MeCN 932.4.3 C—O, C—S Bond Formation in MeCN 962.4.4 C-Halogen Bond Formation in MeCN 982.5 Conclusion 102References 1023 Recent Achievements in Organic Reactions in Bio-based Solvents 107Shaomin Chen, Noman Haider Tariq, and Yanlong Gu3.1 Introduction 1073.2 Glycerol 1083.3 Polyethylene Glycols (PEGs) 1123.4 2-Methyltetrahydrofuran (2-MeTHF) 1143.5 Cyclopentyl Methyl Ether (CPME) 1173.6 Organic Carbonates 1203.7 γ-Valerolactone (GVL) 1253.8 Ethyl Lactate (EL) 1283.9 Miscellaneous 1303.10 Conclusions and Outlook 131References 1314 Recent Achievements in Organic Reactions in DMSO 137Peng Yuan, Jia-Chen Xiang, and An-Xin Wu4.1 Pummerer-type Activation of DMSO 1384.2 Selectfluor-enabled Activation of DMSO 1484.3 Activation of DMSO Enabled by Single-electron Transformation 1514.4 Electrocatalytic Synthesis Enabled Activation of DMSO 1634.5 Photocatalytic Reaction Enabled Activation of DMSO 1644.6 DMSO Acts as the Metal Ligand 1714.7 Some Special Activation or Usage of DMSO 1744.8 Summary and Outlook 181References 1815 The Use of DMC as Green Solvent in Organic Synthesis 185Xinxin Qi and Xiao-Feng Wu5.1 Introduction 1855.2 Organic Reactions in DMC 185References 1976 Applications of Green Deep Eutectic Solvents (DESs) in Synthetic Transformations 199Zhuan Zhang and Taoyuan Liang6.1 Introduction 1996.2 Cross-coupling Reactions in Deep Eutectic Solvents 2016.2.1 C—C Bond Couplings 2016.2.2 C—N Bond Couplings 2106.2.3 C—O Bond Couplings 2116.2.4 C—S Bond Couplings 2126.3 Oxidation Reactions in Deep Eutectic Solvents 2136.3.1 Metal-catalyzed Oxidation 2136.3.2 Other Oxidative Processes 2146.4 Reduction Reactions in Deep Eutectic Solvents 2176.4.1 Metal-catalyzed Reduction 2176.4.2 Other Catalytic Reduction 2186.5 Cyclization Reactions in Deep Eutectic Solvents 2196.5.1 Synthesis of Five-membered Ring 2196.5.2 Synthesis of Six-membered Ring 2206.6 Condensation Reactions in Deep Eutectic Solvents 2216.6.1 DES as the Catalyst/Solvent System for Condensation 2216.6.2 Other Catalytic System for Condensation 2236.7 Multicomponent Reactions in Deep Eutectic Solvents 2246.7.1 One-pot Three-component Reaction 2246.7.2 One-pot Four-component Reaction 2276.8 Other Organic Reactions in Deep Eutectic Solvents 2286.8.1 Isomerization Reaction 2286.8.2 Ring-opening Reaction 2306.8.3 Esterification Reaction 2306.9 Polymerization in DSEs 2316.9.1 Anionic Polymerization of Alkenes 2316.9.2 Glycolysis and Polyesterification 2316.9.3 Oxidative Polymerization 2326.9.4 Visible-light-driven RAFT Polymerization 2326.10 Conclusion 233References 2337 Recent Achievements in Organic Reactions in Ionic Liquids 237Jianxiao Li and Huanfeng Jiang7.1 Introduction 2377.2 Transition Metal-catalyzed Reactions 2387.2.1 Palladium-catalyzed Cascade Cyclization Reaction 2397.2.2 Carbonylation Reactions 2487.2.3 Sonogashira Coupling Reactions 2527.2.4 Suzuki Coupling Reactions 2557.2.5 Copper-catalyzed Coupling Reactions 2577.3 Outlook 259List of Abbreviations 259References 2608 Recent Achievements in Organic Reactions in Ketones and Esters 263Fan-Lin Zeng and Bing Yu8.1 Introduction 2638.2 Organic Reactions in Ketones 2638.2.1 Organic Reactions in Cyrene 2638.2.2 Organic Reactions in NBP 2668.3 Organic Reactions in Esters 2688.3.1 Organic Reactions in Organic Carbonates 2688.3.2 Organic Reactions in γ-Valerolactone 2708.3.3 Organic Reactions in Ethyl Lactate 2738.4 Conclusion 275References 2759 Recent Achievements in Organic Reactions in Polyethylene Glycol 279Zhiping Yin9.1 Introduction 2799.2 PEG in Pd-catalyzed Coupling Reactions 2809.2.1 Pd-catalyzed C—C, C—Si Bonds Formation in PEG 2809.2.2 Pd-catalyzed C—N, C—P Bond Formation in PEG 2909.2.3 Pd-catalyzed C—O Bond Formation in PEG 2919.2.4 Pd-catalyzed C—B Bond Formation in PEG 2919.3 PEG in Cu-catalyzed Reactions 2929.3.1 Cu-catalyzed C—C Bond Formation in PEG 2929.3.2 Cu-catalyzed C—N Bond Formation in PEG 2939.3.3 Cu-catalyzed C—O, C—S, and C—Se Bond Formation in PEG 2969.4 PEG in Ni, Ru, and Pt-catalyzed Reactions 2999.5 PEG in Organocatalysis Reactions 3029.6 PEG in Multicomponent Reactions 3049.7 PEG in Cyclization Reactions 3069.7.1 Synthesis of Five-membered Ring Systems 3069.7.2 Synthesis of Six and Seven-membered Ring Systems 3089.8 Conclusion 309Acknowledgments 310References 31010 Recent Advances in Organic Reactions Using Water as Solvent 317Chang-Sheng Wang, Qiao Sun, Guowei Wang, Wei He, Zheng Fang, and Kai Guo10.1 Introduction 31710.2 Cross-Coupling Reactions 31810.2.1 C–C Cross-Coupling 31810.2.2 C–N Cross-Coupling 33610.2.3 C–S Cross-Coupling 34210.2.4 C–P Cross-Coupling 34610.3 C–H Functionalization 34710.3.1 C–C Bond Formation 34710.3.2 C–N Bond Formation 36410.3.3 C–O Bond Formation 36710.3.4 C–X Bond Formation 36910.3.5 C–H Annulation/Cyclization 37010.4 C–C Activation 37410.5 C–O Cleavage Reactions 37610.6 Oxidative and Reductive Reactions 37710.6.1 Electrochemical Oxidation 37710.6.2 Reduction and Related Reactions 37910.7 Substitution Reactions 38110.7.1 Nucleophilic Substitution 38110.7.2 Electrophilic Substitution 38310.7.3 Radical Substitution 38410.8 Addition Reactions 38610.8.1 Nucleophilic Addition 38610.8.2 Alkene/Alkyne Functionalization via Radical Addition 39210.8.3 Alkene or Alkyne Functionalization via Radical-Free Addition 39610.8.4 Cycloaddition Reactions 39910.9 Cyclization or Annulation Reactions 40310.9.1 Radical-Free Cyclization/Annulation 40310.9.2 Radical Cyclization 40610.10 Multicomponent Reaction (MCR) 41010.11 Domino/Tandem/Cascade Reactions 41710.11.1 Chemo-Domino/Tandem/Cascade Reactions 41710.11.2 Chemoenzymatic Reactions 42210.12 Rearrangement or Insertion Reactions 42510.12.1 Rearrangement Reactions 42510.12.2 Carbene Insertion/Transfer Reactions 42910.13 Amide Condensation Reactions 43110.14 Summary and Conclusions 435Acknowledgments 435References 435Index 443