Green Solvents in Organic Synthesis

Essential reference on replacing conventional solvents with greener alternatives in industrial chemicals synthesis and production

A well-timed book promoting sustainability in synthesis and production of chemicals, Green Solvents in Organic Synthesis details various green solvents, solvent systems, and solubilization techniques, including their chemistry, physiochemical properties, performance, and distinct applications, presenting a greener approach to conventional solvents by replacing them with sustainable alternatives that have similarities in their reaction mechanisms.

Edited by four highly qualified academics with significant research experience in the field, Green Solvents in Organic Synthesis includes information on:

• Water and liquid polymers (Polyethylene glycol PEG), Acetonitrile, DMSO, Dimethyl carbonate, Ionic liquids, and Supercritical fluids)
• Bio-based solvents (Cyrene, ?-Valerolactone (GVL), Lactic acid, 2-MeTHF) and deep eutectic solvents (DESs)
• Alcohols (MeOH, EtOH, i-PrOH, n-BuOH, t-BuOH, Ethylene glycol), ketones (Acetones, MEK, MIBK, Cyclohexanone), and esters (Methyl acetate, Ethyl acetate, i-PrOAc, n-BuOAc)
• Technical, economic, and environmental aspects of green solvents and how to maximize their reuse and recycling to alleviate pollution and reduce energy consumption

For chemists in a variety of disciplines, Green Solvents in Organic Synthesis is an essential reference that provides foundational knowledge of green solvents, along with key features of each class of green solvent within the context of organic reactions for industrial and laboratory synthesis.

1 Recent Achievements in Organic Reactions in Alcohols 1
Lan Zhao, Man Zhao, Meng-Ge Wei, Hong-Ru Li, and Liang-Nian He

1.1 Introduction 1

1.2 Alcohols as Green Solvents 6

1.2.1 Hydrogenation/Reduction Reaction 6

1.2.2 Oxidation Reaction 8

1.2.3 Substitution Reaction 10

1.2.4 Addition Reaction 11

1.2.5 Cyclization Reaction 13

1.2.6 Coupling Reaction 18

1.2.7 Condensation/Ring Condensation Reaction 21

1.3 Alcohols as Green Solvents and Catalysts 28

1.3.1 Addition Reaction 28

1.3.2 Cyclization Reaction 28

1.3.3 Coupling Reaction 30

1.3.4 Condensation Reaction 30

1.3.5 Metathesis Reaction 35

1.4 Alcohols as Green Solvents and Hydrogen Donors 35

1.5 Miscellaneous 39

1.5.1 Polyethylene Glycol as a Solvent for CO 2 Capture and Conversion 39

1.5.2 Polyethylene Glycol Radical-Initiated Oxidation Reactions in Compressed Carbon Dioxide 41

1.5.3 Ring-Opening Reaction 43

1.6 Summary and Concluding Remarks 45

Acknowledgments 46

References 46

2 Recent Achievements in Organic Reactions in MeCN 51
Tongtong Xing, Guizhi Zhai, Linna Wu, Xiaofen Wang, and Zechao Wang

2.1 Introduction 51

2.2 MeCN in Transition Metal-catalyzed Reactions Without Radicals Involved 52

2.2.1 Transition Metal-catalyzed Addition Reactions in MeCN 52

2.2.2 Transition Metal-catalyzed Oxidation Reactions in MeCN 56

2.2.3 Transition Metal-catalyzed Reduction Reactions in MeCN 64

2.2.4 Transition Metal-catalyzed Substitution Reactions in MeCN 66

2.2.5 Transition Metal-catalyzed Cyclization Reactions in MeCN 74

2.3 MeCN in Transition Metal-free Catalyzed Reactions Without Radicals Involved 80

2.3.1 Transition Metal-free Catalyzed Cyclization Reactions in MeCN 80

2.3.2 Transition Metal-free Catalyzed Multicomponent Reactions in MeCN 84

2.3.3 Transition Metal-free Catalyzed C—X Bond Formation in MeCN 87

2.4 MeCN in C—X Bonds Formation With Radicals Involved 90

2.4.1 C—C, C—Si Bond Formation in MeCN 90

2.4.2 C—N, C—P Bond Formation in MeCN 93

2.4.3 C—O, C—S Bond Formation in MeCN 96

2.4.4 C-Halogen Bond Formation in MeCN 98

2.5 Conclusion 102

References 102

3 Recent Achievements in Organic Reactions in Bio-based Solvents 107
Shaomin Chen, Noman Haider Tariq, and Yanlong Gu

3.1 Introduction 107

3.2 Glycerol 108

3.3 Polyethylene Glycols (PEGs) 112

3.4 2-Methyltetrahydrofuran (2-MeTHF) 114

3.5 Cyclopentyl Methyl Ether (CPME) 117

3.6 Organic Carbonates 120

3.7 γ-Valerolactone (GVL) 125

3.8 Ethyl Lactate (EL) 128

3.9 Miscellaneous 130

3.10 Conclusions and Outlook 131

References 131

4 Recent Achievements in Organic Reactions in DMSO 137
Peng Yuan, Jia-Chen Xiang, and An-Xin Wu

4.1 Pummerer-type Activation of DMSO 138

4.2 Selectfluor-enabled Activation of DMSO 148

4.3 Activation of DMSO Enabled by Single-electron Transformation 151

4.4 Electrocatalytic Synthesis Enabled Activation of DMSO 163

4.5 Photocatalytic Reaction Enabled Activation of DMSO 164

4.6 DMSO Acts as the Metal Ligand 171

4.7 Some Special Activation or Usage of DMSO 174

4.8 Summary and Outlook 181

References 181

5 The Use of DMC as Green Solvent in Organic Synthesis 185
Xinxin Qi and Xiao-Feng Wu

5.1 Introduction 185

5.2 Organic Reactions in DMC 185

References 197

6 Applications of Green Deep Eutectic Solvents (DESs) in Synthetic Transformations 199
Zhuan Zhang and Taoyuan Liang

6.1 Introduction 199

6.2 Cross-coupling Reactions in Deep Eutectic Solvents 201

6.2.1 C—C Bond Couplings 201

6.2.2 C—N Bond Couplings 210

6.2.3 C—O Bond Couplings 211

6.2.4 C—S Bond Couplings 212

6.3 Oxidation Reactions in Deep Eutectic Solvents 213

6.3.1 Metal-catalyzed Oxidation 213

6.3.2 Other Oxidative Processes 214

6.4 Reduction Reactions in Deep Eutectic Solvents 217

6.4.1 Metal-catalyzed Reduction 217

6.4.2 Other Catalytic Reduction 218

6.5 Cyclization Reactions in Deep Eutectic Solvents 219

6.5.1 Synthesis of Five-membered Ring 219

6.5.2 Synthesis of Six-membered Ring 220

6.6 Condensation Reactions in Deep Eutectic Solvents 221

6.6.1 DES as the Catalyst/Solvent System for Condensation 221

6.6.2 Other Catalytic System for Condensation 223

6.7 Multicomponent Reactions in Deep Eutectic Solvents 224

6.7.1 One-pot Three-component Reaction 224

6.7.2 One-pot Four-component Reaction 227

6.8 Other Organic Reactions in Deep Eutectic Solvents 228

6.8.1 Isomerization Reaction 228

6.8.2 Ring-opening Reaction 230

6.8.3 Esterification Reaction 230

6.9 Polymerization in DSEs 231

6.9.1 Anionic Polymerization of Alkenes 231

6.9.2 Glycolysis and Polyesterification 231

6.9.3 Oxidative Polymerization 232

6.9.4 Visible-light-driven RAFT Polymerization 232

6.10 Conclusion 233

References 233

7 Recent Achievements in Organic Reactions in Ionic Liquids 237
Jianxiao Li and Huanfeng Jiang

7.1 Introduction 237

7.2 Transition Metal-catalyzed Reactions 238

7.2.1 Palladium-catalyzed Cascade Cyclization Reaction 239

7.2.2 Carbonylation Reactions 248

7.2.3 Sonogashira Coupling Reactions 252

7.2.4 Suzuki Coupling Reactions 255

7.2.5 Copper-catalyzed Coupling Reactions 257

7.3 Outlook 259

List of Abbreviations 259

References 260

8 Recent Achievements in Organic Reactions in Ketones and Esters 263
Fan-Lin Zeng and Bing Yu

8.1 Introduction 263

8.2 Organic Reactions in Ketones 263

8.2.1 Organic Reactions in Cyrene 263

8.2.2 Organic Reactions in NBP 266

8.3 Organic Reactions in Esters 268

8.3.1 Organic Reactions in Organic Carbonates 268

8.3.2 Organic Reactions in γ-Valerolactone 270

8.3.3 Organic Reactions in Ethyl Lactate 273

8.4 Conclusion 275

References 275

9 Recent Achievements in Organic Reactions in Polyethylene Glycol 279
Zhiping Yin

9.1 Introduction 279

9.2 PEG in Pd-catalyzed Coupling Reactions 280

9.2.1 Pd-catalyzed C—C, C—Si Bonds Formation in PEG 280

9.2.2 Pd-catalyzed C—N, C—P Bond Formation in PEG 290

9.2.3 Pd-catalyzed C—O Bond Formation in PEG 291

9.2.4 Pd-catalyzed C—B Bond Formation in PEG 291

9.3 PEG in Cu-catalyzed Reactions 292

9.3.1 Cu-catalyzed C—C Bond Formation in PEG 292

9.3.2 Cu-catalyzed C—N Bond Formation in PEG 293

9.3.3 Cu-catalyzed C—O, C—S, and C—Se Bond Formation in PEG 296

9.4 PEG in Ni, Ru, and Pt-catalyzed Reactions 299

9.5 PEG in Organocatalysis Reactions 302

9.6 PEG in Multicomponent Reactions 304

9.7 PEG in Cyclization Reactions 306

9.7.1 Synthesis of Five-membered Ring Systems 306

9.7.2 Synthesis of Six and Seven-membered Ring Systems 308

9.8 Conclusion 309

Acknowledgments 310

References 310

10 Recent Advances in Organic Reactions Using Water as Solvent 317
Chang-Sheng Wang, Qiao Sun, Guowei Wang, Wei He, Zheng Fang, and Kai Guo

10.1 Introduction 317

10.2 Cross-Coupling Reactions 318

10.2.1 C–C Cross-Coupling 318

10.2.2 C–N Cross-Coupling 336

10.2.3 C–S Cross-Coupling 342

10.2.4 C–P Cross-Coupling 346

10.3 C–H Functionalization 347

10.3.1 C–C Bond Formation 347

10.3.2 C–N Bond Formation 364

10.3.3 C–O Bond Formation 367

10.3.4 C–X Bond Formation 369

10.3.5 C–H Annulation/Cyclization 370

10.4 C–C Activation 374

10.5 C–O Cleavage Reactions 376

10.6 Oxidative and Reductive Reactions 377

10.6.1 Electrochemical Oxidation 377

10.6.2 Reduction and Related Reactions 379

10.7 Substitution Reactions 381

10.7.1 Nucleophilic Substitution 381

10.7.2 Electrophilic Substitution 383

10.7.3 Radical Substitution 384

10.8 Addition Reactions 386

10.8.1 Nucleophilic Addition 386

10.8.2 Alkene/Alkyne Functionalization via Radical Addition 392

10.8.3 Alkene or Alkyne Functionalization via Radical-Free Addition 396

10.8.4 Cycloaddition Reactions 399

10.9 Cyclization or Annulation Reactions 403

10.9.1 Radical-Free Cyclization/Annulation 403

10.9.2 Radical Cyclization 406

10.10 Multicomponent Reaction (MCR) 410

10.11 Domino/Tandem/Cascade Reactions 417

10.11.1 Chemo-Domino/Tandem/Cascade Reactions 417

10.11.2 Chemoenzymatic Reactions 422

10.12 Rearrangement or Insertion Reactions 425

10.12.1 Rearrangement Reactions 425

10.12.2 Carbene Insertion/Transfer Reactions 429

10.13 Amide Condensation Reactions 431

10.14 Summary and Conclusions 435

Acknowledgments 435

References 435

Index 443

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.