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Green Techniques for Organic Synthesis and Medicinal Chemistry, 2nd Edition

Green Techniques for Organic Synthesis and Medicinal Chemistry, 2nd Edition

Wei Zhang (Editor), Berkeley W. Cue (Editor)

ISBN: 978-1-119-28815-2

Feb 2018

728 pages

Description

An updated overview of the rapidly developing field of green techniques for organic synthesis and medicinal chemistry

Green chemistry remains a high priority in modern organic synthesis and pharmaceutical R&D, with important environmental and economic implications. This book presents comprehensive coverage of green chemistry techniques for organic and medicinal chemistry applications, summarizing the available new technologies, analyzing each technique’s features and green chemistry characteristics, and providing examples to demonstrate applications for green organic synthesis and medicinal chemistry.  

The extensively revised edition of Green Techniques for Organic Synthesis and Medicinal Chemistry includes 7 entirely new chapters on topics including green chemistry and innovation, green chemistry metrics, green chemistry and biological drugs, and the business case for green chemistry in the generic pharmaceutical industry. It is divided into 4 parts. The first part introduces readers to the concepts of green chemistry and green engineering, global environmental regulations, green analytical chemistry, green solvents, and green chemistry metrics. The other three sections cover green catalysis, green synthetic techniques, and green techniques and strategies in the pharmaceutical industry.

  • Includes more than 30% new and updated material—plus seven brand new chapters
  • Edited by highly regarded experts in the field (Berkeley Cue is one of the fathers of Green Chemistry in Pharma) with backgrounds in academia and industry
  • Brings together a team of international authors from academia, industry, government agencies, and consultancies (including John Warner, one of the founders of the field of Green Chemistry)

Green Techniques for Organic Synthesis and Medicinal Chemistry, Second Edition is an essential resource on green chemistry technologies for academic researchers, R&D professionals, and students working in organic chemistry and medicinal chemistry.

List of Contributors xvii

Foreword xxi

Preface xxiii

Part I General Topics in Green Chemistry 1

Green ChemistryMetrics 3
Frank Roschangar and Juan Colberg

1.1 Business Case 3

1.2 Historical Context 3

1.3 Metrics, Awards, and Barriers 4

1.4 Metrics Unification Via Green Aspiration Level 9

1.5 Green Scorecard 12

1.6 Supply Chain 14

1.7 Outlook and Opportunities 15

References 17

Green Solvents 21
Janet L. Scott and Helen F. Sneddon

2.1 Introduction 21

2.2 Solvent Selection Guides and Tools 23

2.3 Greener Molecular Solvents 24

2.4 Opportunities, Challenges, and Future Developments 34

References 34

Green Analytical Chemistry 43
Paul Ferguson and Douglas Raynie

3.1 Introduction 43

3.2 Sample Preparation 47

3.3 Techniques and Methods 50

3.4 Process Analytical Technology 60

3.5 Biopharmaceutical Analysis 62

3.6 Conclusions 65

Acknowledgments 66

References 66

Green Engineering 71
Christopher L. Kitchens and Lindsay Soh

4.1 Introduction: Green Engineering Misconceptions and Realizations 71

4.2 12 Principles of Green Engineering 72

4.3 Green Chemistry Metrics Applied to Engineering 73

4.4 Use of Green Solvents in the Chemical Industry 80

4.5 Presidential Green Chemistry Awards 86

4.6 Opportunities and Outlook 87

References 87

Greening of Consumer Cleaning Products 91
David C. Long

5.1 History of Green Consumer Cleaning Products 91

5.2 Drivers for Greener Products 94

5.3 Development of Green Cleaning Criteria and Eco-Labeling 98

5.4 Development of Greener Ingredients for Cleaners 102

5.5 The Future of Green Cleaning 111

Acknowledgments 112

References 112

Innovation with Non-Covalent Derivatization 117
John C.Warner and Emily Stoler

6.1 Introduction 117

6.2 NCD Overview 118

6.3 Pharmaceutical NCDs 121

6.4 Environmental and Green Chemistry Benefits 123

References 123

Part II Green Catalysts 131

Catalytic C-H Bond Cleavage for Heterocyclic Compounds 133
Zhanxiang Liu and Yuhong Zhang

7.1 Introduction 133

7.2 Synthesis of Nitrogen Heterocycles 133

7.3 Synthesis of Oxygen-Containing Heterocycles 144

7.4 Synthesis of Sulfur-Containing Heterocycles 148

7.5 Medium-Sized Heterocyclic Compounds 150

7.6 Conclusion 152

References 152

Biocatalysis 161
James Lalonde

8.1 Introduction 161

8.2 Enzymes for Biocatalysis 162

8.3 Advances in Enzyme Engineering and Directed Evolution 164

8.4 Biocatalytic Synthesis of Pharmaceuticals: Case Studies of Highly Efficient Pharmaceutical Syntheses 165

8.5 Summary and Future Outlook 178

References 180

Practical Asymmetric Organocatalysis 185
Wen-Zhao Zhang, Samik Nanda, and Sanzhong Luo

9.1 Introduction 185

9.2 Aminocatalysis 185

9.3 Brønsted Acid Catalysis 191

9.4 Brønsted Base Catalysis 193

9.5 Hydrogen-Bonding Catalysis 197

9.6 Phase-Transfer Catalysis 202

9.7 Lewis Acid, Lewis Base, and N-Heterocyclic Carbene Catalysis 204

9.8 Large-Scale Reaction (>100-Gram Reaction) 207

9.9 Conclusion 209

References 209

Fluorous Catalysis 219
L´aszl´o T. Mika and Istv´an T. Horv´ath

10.1 Introduction and the Principles of Fluorous Catalysis 219

10.2 Ligands for Fluorous Transition Metal Catalysts 224

10.3 Synthetic Application of Fluorous Catalysis 225

10.4 Fluorous Organocatalysis 256

10.5 Other Applications of Fluorous Catalysis 259

References 259

Solid-Supported Catalysis 269
Sukanta Bhattacharyya and Basudeb Basu

11.1 Introduction 269

11.2 Immobilized Palladium Catalysts 270

11.3 Immobilized Rhodium Catalysts 276

11.4 Immobilized Ruthenium Catalysts 279

11.5 Other Immobilized Catalysts 284

11.6 Conclusions 286

References 287

Asymmetric Organocatalysis in Aqueous Media 291
Kartick C. Bhowmick and Tanmoy Chanda

12.1 Introduction 291

12.2 Carbon-Carbon Bond-Formation Reactions 292

12.3 Reactions Other than C-C Bond Formation 313

12.4 Conclusion 314

References 314

Part III Green Synthetic Techniques 325

Solvent-Free Synthesis 327
Kendra Leahy Denlinger and JamesMack

13.1 Introduction 327

13.2 Ball Milling 328

References 339

Ultrasonic Reactions 343
Rodrigo Cella and H´elio A. Stefani

14.1 Introduction 343

14.2 How Does CavitationWork? 343

14.3 Aldol/Condensation Reactions 345

14.4 1,4-Addition 351

14.5 Heterocycles Synthesis 353

14.6 Coupling Reactions 356

14.7 Wittig Reaction 361

14.8 Diels-Alder Reaction 362

14.9 Miscellaneous 365

14.10 Conclusions 366

References 366

Photochemical Synthesis 373
Stefano Protti,Maurizio Fagnoni, and Angelo Albini

15.1 Introduction 373

15.2 Synthesis and Rearrangement of Open-Chain Compounds 376

15.3 Synthesis of Three- and Four-Membered Rings 382

15.4 Synthesis of Five-, Six- (and Larger)-Membered Rings 391

15.5 Oxygenation and Oxidation 398

15.6 Conclusions 400

Acknowledgments 401

References 401

Pot Economy Synthesis 407
Wenbin Yi, Xin Zeng, and Song Gao

16.1 Introduction 407

16.2 Multicomponent Reactions 407

16.3 One-Pot and Multi-Step Reactions 415

16.4 One-Pot Asymmetric Synthesis 424

16.5 Outlook 434

References 434

Microwave-Assisted Organic Synthesis: Overview of Recent Applications 441
Nandini Sharma, Upendra K. Sharma, and Erik V. Van der Eycken

17.1 Introduction 441

17.2 C-H Functionalization 449

17.3 Insertion Reactions 452

17.4 Reduction 453

17.5 Synthesis of Peptides and Related Fine Chemicals 455

17.6 Newer Developments 459

17.7 Summary 461

References 461

Solid-Supported Synthesis 469
Indrajeet J. Barve and Chung-Ming Sun

Abbreviations 469

18.1 Introduction 471

18.2 Techniques of Solid-Phase Supported Synthesis 472

18.3 Solid-Phase Supported Heterocyclic Chemistry 476

18.4 Solid-Supported Synthesis of Natural Products 486

18.5 Solid-Supported Organometallic Chemistry 491

18.6 Solid-Phase Synthesis of Peptides 493

18.7 Solid-Phase Supported Stereoselective Synthesis 494

18.8 Interdisciplinary Solid-Supported Synthesis 499

References 505

Light Fluorous Synthesis 509
Wei Zhang

19.1 Introduction 509

19.2 “Heavy” Versus “Light” Fluorous Chemistry 509

19.3 The Green Chemistry Aspects of Fluorous Synthesis 510

19.4 Fluorous Techniques for Discovery Chemistry 511

19.5 Conclusions 533

References 533

Part IV Green Techniques and Strategies in the Pharmaceutical Industry 539

Ionic Liquids in Pharmaceutical Industry 541
Julia L. Shamshina, Paula Berton, HuiWang, Xiaosi Zhou, Gabriela Gurau, and Robin D. Rogers

Abbreviations 541

20.1 Introduction 543

20.2 Finding the Right Role for ILs in the Pharmaceutical Industry 544

20.3 Conclusions and Prospects 567

References 568

Green Technologies and Approaches in theManufacture of Biologics 579
Sa V. Ho and Kristi L. Budzinski

21.1 Introduction 579

21.2 Characteristics of Biologics 580

21.3 Manufacture of Therapeutic Biologics 581

21.4 Environmental Metrics Development and Impact Analysis 587

21.5 Some Future Directions 592

21.6 Conclusions 594

Acknowledgments 594

References 594

Benchmarking Green Chemistry Adoption by “Big Pharma”and Generics Manufacturers 601
Vesela R. Veleva and BerkeleyW. Cue

22.1 Introduction 601

22.2 Literature Review 602

22.3 Pharmaceutical Industry Overview and Green Chemistry Drivers 604

22.4 Benchmarking Industry Adoption of Green Chemistry 607

22.5 Results and Discussion 610

22.6 Conclusion 616

References 616

Green Process Chemistry in the Pharmaceutical Industry: Case Studies Update 621
Joseph M. Fortunak, Ji Zhang, Frederick E. Nytko III, and Tiffany N. Ellison

23.1 Introduction 621

23.2 Pharmaceutical Patents Driving Innovation 622

23.3 A Caution About Drug Manufacturing Costs 623

23.4 Process Evolution by Multiple Route Discovery Efforts—Dolutegravir 624

23.5 The Impact of Competition on Process Evolution—Tenofovir Disoproxil Fumarate 628

23.6 Simeprevir (Olysio/Sovriad) and Analogues: Chiral Phase-Transfer Catalyst-Promoted Optical Alpha-Amino Acid Synthesis: A Metal-free Process 633

23.7 Vaniprevir (MK 7009), Simeprevir (TMC435), and Danoprevir: Ring-Closing Metathesis (RCM) for Macrocyclic Lactam Synthesis: Now a Commercial Reality 635

23.8 Daclatasvir (BMS-790052, Daklinza), and Ledipasvir (GS-5885): Palladium Catalyzed Cross-Coupling for Greening a Process 638

23.9 Sitagliptin (Januvia) and Ponatinib (Iclusig): Greening the Process by Telescoping Multiple Steps Together 639

23.10 Febuxostat (Uloric): Greening the Process via Metal Catalyzed C-H Activation: A Prospect 641

23.11 Conclusions 644

References 644

Greener Pharmaceutical Science Through Collaboration: The ACS GCI Pharmaceutical Roundtable 649
Julie B. Manley andMichael E. Kopach

24.1 Introduction 649

24.2 Establishing Pre-Competitive Collaborations 650

24.3 Informing and Influencing the Research Agenda 654

24.4 Developing Tools 661

24.5 Educating Leaders 666

24.6 Collaborating Globally 668

24.7 Future Opportunities 669

24.8 Success Factors 671

References 673

Index 675