Green chemistry has played a leading role in the broader search for environmentally sustainable industry. One of its most important goals is the shift from volatile, hazardous organic solvents to environmentally friendly ones, of which by far the most promising is water. Cultivating organic transformations using water as a solvent is one of the most crucial steps towards the creation of green, sustainable chemical production processes.
Organic Transformations in Water provides a cutting-edge overview of water as a reaction medium for synthesis and catalysis. After a brief introduction, the book moves through each of the most important classes of organic transformation before concluding with a survey of industrial applications.
The book will also cover: - Chemistry and physicochemical aspects of “on-water” and “in-water” reactions- C-H activation, metathesis, nucleophilic addition and substitution, oxidation and reduction, and many more- Asymmetric organic reactions in water- Applications in organocatalysis, electrocatalysis, and photocatalysis
Timely and comprehensive, Organic Transformations in Water is a must-own volume for researchers and industry professionals looking to revolutionize their work in a sustainable way.
Table of Contents
About the Editors xvii
Preface xix
List of Abbreviations xxi
1 An Introduction to Organic Transformations in Water 1
Nissy Ann Harry and Gopinathan Anilkumar
1.1 The Emergence of Water as a Solvent in Organic Chemistry 1
1.2 Green Chemistry and Water 3
1.3 Conclusion 8
References 9
2 Chemistry of “On-Water” Reactions 11
Anthony G. Coyne
2.1 Introduction 11
2.2 Broadening the Scope of On-Water Reactions 20
2.3 Conclusions 25
References 25
3 Chemistry of “In-Water” Reactions: Spotlights on Micellar and Phase-Transfer Catalysis 29
Tharique N. Ansari, Gaganpreet Kaur, Thomas J. Colacot, and Sachin Handa
3.1 Introduction 29
3.2 Understanding the Concept of Micellar Catalysis 30
3.3 Basic Principles of Phase-Transfer Catalysis 31
3.4 Highlights of Micellar Catalysis 32
3.5 Highlights of PTC 52
3.6 Conclusion 56
References 56
4 Physicochemical Aspects of “On-Water” and “In-Water” Reactions 63
Rachel Napier and Bao N. Nguyen
4.1 Introduction 63
4.2 Phase Behaviors of Realistic Reactions 64
4.3 Mechanistic Considerations 68
4.4 Green Processes Based on Water-Accelerated Reactions 79
4.5 Summary and Conclusions 80
References 80
5 C-H Activation Reactions in Aqueous Medium 83
Feng Zhou and Chao-Jun li
5.1 Introduction 83
5.2 C-H Bond Activation Reactions in Aqueous Medium 84
5.3 Summary and Conclusion 100
Acknowledgments 101
References 101
6 Recent Developments in Multicomponent Reactions in Water 105
Bibi E. M. Nanlohy and Floris P. J. T. Rutjes
6.1 Introduction 105
6.2 I-MCRs 108
6.3 Knoevenagel-Initiated MCRs 119
6.4 Summary and Conclusions 135
References 135
7 Pericyclic Reactions in Aqueous Medium 141
Surabhi Mishra, Sumran Raikwar, and Beeraiah Baire
7.1 Introduction 141
7.2 Cycloaddition Reactions in Aqueous Medium 143
7.3 Miscellaneous Cycloaddition Reactions In-Water 150
7.4 Electrocyclic Reactions In-Water (Ring Closure and Ring Opening) 154
7.5 Sigmatropic Rearrangements In-Water 156
7.6 Ene Reactions 157
7.7 Summary and Conclusions 158
References 158
8 Olefin Metathesis In-Water: Recent Progress and Challenges 165
Bengi Özgün Öztürk
8.1 Introduction 165
8.2 Ionic, Non-Ionic, and Amphiphilic Group-Tagged Olefin Metathesis Catalysts 166
8.3 Biopolymer Integrated Olefin Metathesis Catalysts 175
8.4 Conclusion 176
Acknowledgments 177
References 177
9 Oxidation and Reduction Reactions in Water 179
Rose Mary Philip, Padinjare Veetil Saranya, and Gopinathan Anilkumar
9.1 Introduction 179
9.2 Oxidation Reactions in Water 180
9.3 Reduction Reactions in Water 185
9.4 Summary and Conclusions 193
References 194
10 Radical Reactions in Water 197
Xiaoye Yu, Ying Zhang, and Huan-Ming Huang
10.1 Introduction 197
10.2 Transition Metal-Catalyzed Radical Reaction in Water 198
10.3 Transition Metal-Free Radical Reaction in Water 203
10.4 Photoredox Reactions Excited by Visible Light in Water 212
10.5 Conclusions 218
References 218
11 Carbene Reactions in Water 223
Xiaoye Yu, Ying Zhang, and Huan-Ming Huang
11.1 Introduction 223
11.2 Carbene Reaction in Water 223
11.3 Conclusions 228
References 229
12 Nucleophilic Addition and Substitution Reactions In-Water 231
Panackalchirayil S. Devi, Pulluparambil X. T. Rinu, and Gopinathan Anilkumar
12.1 Introduction 231
12.2 Nucleophilic Addition Reactions 232
12.3 Nucleophilic Substitution Reactions 240
12.4 Summary and Conclusions 246
References 247
13 Asymmetric Organic Reactions in Water 251
Han-Yong Bae, Woo-Hee Kim, and Seok-Ju Hong
13.1 Introduction 251
13.2 Asymmetric Metal (Lewis Acid) Catalysis in Water 252
13.3 Asymmetric Lewis Base Organocatalysis in Water 258
13.4 Asymmetric Brønsted Acid Organocatalysis in Water 261
13.5 Asymmetric Brønsted Base Organocatalysis in Water 262
13.6 Summary and Conclusions 265
Acknowledgments 266
References 266
14 Organocatalytic Reactions in Water 269
Bubun Banerjee, Anu Priya, Zsuzsanna Szalai, Aditi Sharma, Manmeet Kaur, Arvind Singh, and György Keglevich
14.1 Introduction 269
14.2 Organocatalyzed Synthesis of Biologically Promising N-Heterocycles in Water 270
14.3 Organocatalyzed Synthesis of Biologically Promising O-Heterocycles in Water 274
14.4 Organocatalyzed Synthesis of Biologically Promising N,O-Heterocycles in Water 278
14.5 Organocatalyzed Synthesis of Biologically Promising N,S-Heterocycles in Water 279
14.6 Organocatalyzed Miscellaneous Reactions in Water 280
14.7 Asymmetric Synthesis Using Organocatalysts 283
14.8 Conclusions 288
Acknowledgments 288
References 288
15 Organic Electrocatalysis in Water 291
Samina Aslam, Sadia Rani, Kiran Lal, and Nisar Ahmed
15.1 Introduction 291
15.2 Direct vs. Mediated Reductive Oxidation and Oxidative Reduction 292
15.3 Water as a Solvent and an Electrolyte 292
15.4 Electrocatalysis 294
15.5 Water Electrolysis 295
15.6 Organic Transformations in Water: Principles and Applications 297
15.7 Benefits of Electrochemical Conversions 309
15.8 Conclusion 309
15.9 Future Perspectives 310
References 310
16 Visible Light Photocatalysis in Water 313
Camilla Russo, Francesca Brunelli, Gian Cesare Tron, and Mariateresa Giustiniano
16.1 Introduction 313
16.2 In-Water Reactions 314
16.3 On-Water Reactions 318
16.4 Photobiocatalysis 321
16.5 Summary and Conclusions 325
References 326
17 Industrial Applications of Organic Reactions in Water 329
Chitrakar Ravi and Subbarayappa Adimurthy
17.1 Introduction 329
17.2 Oxidative Esterification of Alcohols 330
17.3 Green Oxidation of Methylarenes to Benzoic Acids with Bromide/Bromate in Water 331
17.4 Environment-Friendly Synthesis of Bromoxynil and Iodoxynil 332
17.5 Synthesis of 2,6-Dibromo-4-Nitroaniline from 4-Nitroaniline in an Aqueous Medium 333
17.6 HBr-H2 O2 for Regioselective Synthesis of Bromohydrins and α-Bromoketones and Oxidation of Benzylic/Secondary Alcohols to Carbonyl Compounds in Aqueous Medium 334
17.7 Water-Mediated Synthesis of Imidazo[1,2-a]Pyridines 336
17.8 Sulfenylation of N-Heteroarenes in Water (Rice Cooking Method) 337
17.9 Summary and Conclusions 338
Acknowledgments 339
References 339
Index 343
