Sustainable Catalysis - Challenges and Practices for the Pharmaceutical and Fine Chemical Industries

Driven by both public demand and government regulations, pharmaceutical and fine chemical manufacturers are increasingly seeking to replace stoichiometric reagents used in synthetic transformations with catalytic routes in order to develop greener, safer, and more cost-effective chemical processes....

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Bibliographic Details
Main Authors: Dunn, Peter J, Hii, K. K. (Mimi), Krische, Michael J, Williams, Michael T
Format: eBook Book
Language:English
Published: Hoboken, N.J John Wiley & Sons 2013
Wiley
John Wiley & Sons, Incorporated
Wiley-Blackwell
Edition:1
Subjects:
Catalysis
Catalysts
Chemical engineering
Chemistry & Chemical Engineering
Environmental chemistry
Environmental chemistry > Industrial applications
Industrial applications
Pharmaceutical industry
Pharmaceutical industry > Waste minimization
Waste minimization
ISBN:1118155424, 9781118155424, 9781118354513, 1118354516, 9781118354520, 1118354524
Online Access:Get full text
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Table of Contents:
  • Title Page Abbreviations Preface Table of Contents 1. Catalytic Reduction of Amides Avoiding LiAlH4 or B2H6 2. Hydrogenation of Esters 3. Synthesis of Chiral Amines Using Transaminases 4. Development of a Sitagliptin Transaminase 5. Direct Amide Formation Avoiding Poor Atom Economy Reagents 6. Industrial Applications of Boric Acid and Boronic Acid-Catalyzed Direct Amidation Reactions 7. OH Activation for Nucleophilic Substitution 8. Application of a Redox-Neutral Alcohol Amination in the Kilogram-Scale Synthesis of a Glyt1 Inhibitor 9. Olefin Metathesis: From Academic Concepts to Commercial Catalysts 10. Challenge and Opportunity in Scaling-up Metathesis Reaction: Synthesis of Ciluprevir (BILN 2061) 11. C-H Activation of Heteroaromatics 12. The Discovery of a New Pd/Cu Catalytic System for C-H Arylation and its Applications in a Pharmaceutical Process 13. Diarylprolinol Silyl Ethers: Development and Application as Organocatalysts 14. Organocatalysis for Asymmetric Synthesis: From Lab to Factory 15. Catalytic Variants of Phosphine Oxide-Mediated Organic Transformations 16. Formation of C-C Bonds via Catalytic Hydrogenation and Transfer Hydrogenation Index Color Plates
  • 8.5.3 Solvent Optimization and Additional Parameters -- 8.5.4 Kilogram-Scale Runs under Optimized Conditions -- 8.6 MECHANISTIC DISCUSSION -- 8.7 IRIDIUM CONTROL -- 8.8 FINAL COMMENTS -- ACKNOWLEDGMENTS -- REFERENCES -- 9 Olefin Metathesis: From Academic Concepts to Commercial Catalysts -- 9.1 INTRODUCTION -- 9.2 RECOVERY AND REUSE OF RU-BASED METATHESIS CATALYSTS: THE ACADEMICS' VIEW -- 9.3 APPLICATION OF RUTHENIUM METATHESIS CATALYSTS IN WATER -- 9.4 SUMMARY AND OUTLOOK -- ACKNOWLEDGMENTS -- REFERENCES -- 10 Challenge and Opportunity in Scaling-up Metathesis Reaction: Synthesis of Ciluprevir (BILN 2061) -- 10.1 INTRODUCTION -- 10.2 SYNTHESIS OF CILUPREVIR (BILN 2061) AND CRITICAL CHALLENGES -- 10.3 PREPARATIONS OF BUILDING BLOCKS -- 10.4 THE FIRST GENERATION CILUPREVIR (BILN 2061) PROCESS -- 10.5 CHALLENGES IN SCALING UP THE RCM REACTION -- 10.6 DEVELOPMENT OF A PRACTICAL AND SCALABLE RCM PROCESS -- 10.7 THE SECOND GENERATION CILUPREVIR (BILN 2061) PROCESS -- 10.8 CONCLUSION -- REFERENCES -- 11 C-H Activation of Heteroaromatics -- 11.1 INTRODUCTION -- 11.2 DIRECT ARYLATION -- 11.2.1 C - H/ C - X Coupling -- 11.2.2 C - H /C - M Coupling -- 11.2.3 C - H/C - H Coupling -- 11.3 DIRECT ALKENYLATION -- 11.3.1 Coupling with Alkenyl Halides -- 11.3.2 Coupling with Alkenes (Fujiwara - Moritani Reaction) -- 11.3.3 Coupling with Alkynes (Hydroarylation) -- 11.4 DIRECT ALKYNYLATION -- 11.4.1 Coupling with Alkynyl Halides or Pseudohalides -- 11.4.2 Coupling with Terminal Alkynes -- 11.5 DIRECT ALKYLATION -- 11.5.1 Benzylation and Allylation -- 11.5.2 Alkylation with Unactivated Systems -- 11.6 CONCLUSION -- REFERENCES -- 12 The Discovery of a New Pd/Cu Catalytic System for C-H Arylation and Its Applications in a Pharmaceutical Process -- 12.1 INTRODUCTION -- 12.2 DEVELOPMENT OF INITIAL PROCESS FOR THE AGONIST OF S1P1
  • 14.3.2 A Practical Process to Prepare Catalyst DMQ -- 14.3.3 Substrate-Specific Process Evolution -- 14.3.4 Completion of MK-8613 Synthesis -- 14.4 CONCLUSIONS -- ACKNOWLEDGMENTS -- REFERENCES -- 15 Catalytic Variants of Phosphine Oxide-Mediated Organic Transformations -- 15.1 GENERAL INTRODUCTION -- 15.2 WITTIG CHEMISTRY -- 15.3 AZA-WITTIG CHEMISTRY -- 15.4 MITSUNOBU CHEMISTRY -- 15.5 APPEL HALOGENATIONS -- 15.6 CONCLUSIONS -- REFERENCES -- 16 Formation of C-C Bonds Via Catalytic Hydrogenation and Transfer Hydrogenation -- 16.1 INTRODUCTION: MINIMIZING PREACTIVATION FOR SYNTHETIC EFFICIENCY -- 16.2 CARBONYL AND IMINE VINYLATION -- 16.3 CARBONYL ALLYLATION AND PROPARGYLATION -- 16.4 ALDOL, MANNICH, AND RELATED PROCESSES -- 16.5 FUTURE DIRECTIONS -- ACKNOWLEDGMENTS -- REFERENCES -- Index
  • 12.3 DEVELOPMENT OF C - H ARYLATION FOR THE SYNTHESIS OF AMG 369 -- 12.3.1 Initial Results -- 12.3.2 Discovery of a New Cocatalyst -- 12.3.3 Applications to the Synthesis of AMG 369 -- 12.3.4 Latest Developments and Future Perspective -- 12.4 CONCLUSION -- REFERENCES -- 13 Diarylprolinol Silyl Ethers: Development and Application as Organocatalysts -- 13.1 INTRODUCTION AND BACKGROUND -- 13.2 ENAMINE INTERMEDIATE -- 13.2.1 Michael Reaction -- 13.2.2 Acetaldehyde as Nucleophile -- 13.2.3 a-Oxidation Using Benzoyl Peroxide -- 13.2.4 Tandem Reaction Between Nitro-olefin and Pentane-1,5-dial -- 13.2.5 Multicomponent Reactions -- 13.2.6 [6+2] Cycloaddition -- 13.3 IMINIUM ION INTERMEDIATE -- 13.3.1 Diels-Alder and Ene-Type Reactions of Cyclopentadiene -- 13.3.2 Nitroalkane as a Nucleophile -- 13.3.3 Nitroethanol as Nucleophile -- 13.3.4 Formal Aza- and Carbo-[3+3] Cycloaddition -- 13.4 FORMAL C - H INSERTION -- 13.5 REACTIONS IN THE PRESENCE OFWATER -- 13.6 SYNTHESIS OF BIOLOGICALLY ACTIVE MOLECULES -- 13.6.1 Synthesis of ( - )-b-Santalol -- 13.6.2 Synthesis of Oseltamivir -- 13.6.3 Synthesis of ABT-341 (127) -- 13.7 CONCLUSION -- REFERENCES -- 14 Organocatalysis for Asymmetric Synthesis: From Lab to Factory -- 14.1 INTRODUCTION -- 14.2 PREPARATION OF TELCAGEPANT, AN APPLICATION OF IMINIUM ORGANOCATALYSIS -- 14.2.1 Background and Synthetic Strategy -- 14.2.2 Preliminary Results, Identification of By-products, and Reaction Pathway Consideration -- 14.2.3 "Cocktail" Cocatalysts in Non-alcohol Solvents -- 14.2.4 The Use of Crude Jørgensen - Hayashi Catalyst -- 14.2.5 Evolution to a Streamlined Through-process -- 14.2.6 Completion of Telcagepant Synthesis -- 14.3 PREPARATION OF MK-8613, APPLICATION OF ASYMMETRIC MICHAEL ADDITION CATALYZED BY DESMETHYL QUINIDINE -- 14.3.1 Synthetic Target and Strategy Analysis
  • 3.4 TRANSAMINASE-CATALYZED ASYMMETRIC SYNTHESIS OF AMINES -- 3.5 CONCLUSIONS -- REFERENCES -- 4 Development of a Sitagliptin Transaminase -- 4.1 INTRODUCTION -- 4.2 CREATING ACTIVITY -- 4.3 TRANSAMINASE EVOLUTION -- 4.4 PROCESS OPTIMIZATION -- 4.5 A GENERAL AMINATION METHODOLOGY -- 4.6 CONCLUSION AND OUTLOOK -- 4.7 PROCEDURES -- 4.7.1 Transaminase Reaction at 1 kg Reaction Scale -- 4.7.2 FiltrationWorkup -- 4.7.3 Direct Extraction Workup -- REFERENCES -- 5 Direct Amide Formation Avoiding Poor Atom Economy Reagents -- 5.1 INTRODUCTION -- 5.2 MECHANISM FOR BORONIC AND BORIC ACID CATALYSIS -- 5.3 BORIC ACID-BASED CATALYSIS -- 5.4 BORONIC ACID-BASED CATALYSIS -- 5.5 TRIAZINE-BASED REAGENTS -- 5.6 TITANIUM(IV)-BASED REAGENTS -- 5.7 ANTIMONY-BASED REAGENTS -- 5.8 HETEROGENEOUS CATALYSTS AND MICROWAVE-ASSISTED AMIDE SYNTHESIS -- 5.9 SUMMARY AND FUTURE DIRECTIONS -- REFERENCES -- 6 Industrial Applications of Boric Acid and Boronic Acid-Catalyzed Direct Amidation Reactions -- 6.1 INTRODUCTION -- 6.2 THE SYNTHESIS OF EFAPROXIRAL UTILIZING A DIRECT AMIDATION REACTION -- 6.3 DIRECT AMIDATION EXAMPLES FROM DR. REDDY'S LABORATORIES -- 6.4 DIRECT AMIDATION EXAMPLES FROM PFIZER -- 6.5 POTENTIAL TOXICITY OF BORIC ACID -- 6.6 CONCLUSIONS -- ACKNOWLEDGMENT -- REFERENCES -- 7 OH Activation for Nucleophilic Substitution -- 7.1 INTRODUCTION -- 7.2 FORMATION OF C - C BONDS FROM ALCOHOLS -- 7.3 FORMATION OF C - N BONDS FROM ALCOHOLS -- REFERENCES -- 8 Application of a Redox-Neutral Alcohol Amination in the Kilogram-Scale Synthesis of a GlyT1 Inhibitor -- 8.1 INTRODUCTION -- 8.2 BACKGROUND AND INITIAL SYNTHETIC WORK -- 8.3 FIRST-GENERATION SYNTHESIS OF 10 -- 8.4 FIRST APPLICATION OF IR CHEMISTRY AND INITIAL PROCESS DEVELOPMENT EFFORTS -- 8.5 PROCESS OPTIMIZATION OF THE AMINATION REACTION -- 8.5.1 Reliability Optimization -- 8.5.2 Catalyst Loading Optimization
  • SUSTAINABLE CATALYSIS: Challenges and Practices for the Pharmaceutical and Fine Chemical Industries -- Contents -- Foreword -- Preface -- Contributors -- Abbreviations -- 1 Catalytic Reduction of Amides Avoiding LiAlH4 or B2H6 -- 1.1 INTRODUCTION -- 1.2 AMIDES -- 1.3 IMPORTANCE OF AMIDE REDUCTIONS IN PHARMACEUTICAL SYNTHESIS -- 1.4 HETEROGENEOUS AMIDE HYDROGENATION -- 1.5 HOMOGENEOUS AMIDE HYDROGENATION -- 1.5.1 Hydrogenation of Primary Amides -- 1.5.2 Hydrogenation of Secondary Amides -- 1.5.3 Tertiary Amides -- 1.5.4 Scope of Ru/Triphos Amide Hydrogenation -- 1.5.5 Hydrogenation of Diacids in the Presence of Amines -- 1.5.6 Homogeneous Amide Hydrogenation Mechanism -- 1.5.7 Amide C - N Cleavage by Hydrogenation -- 1.6 HYDROSILATION -- 1.6.1 Rhodium-Catalyzed Reduction of Amides Using Silanes -- 1.6.2 Ruthenium-Catalyzed Reduction of Amides Using Silanes -- 1.6.3 Platinum-Catalyzed Reduction of Amides Using Silanes -- 1.6.4 Molybdenum-Catalyzed Reduction of Amides Using Silanes -- 1.6.5 Indium Bromide-Catalyzed Reduction of Amides Using Silanes -- 1.6.6 Iron-Catalyzed Reduction of Amides Using Silanes -- 1.6.7 Zinc-Catalyzed Reduction of Amides Using Silanes -- 1.7 CONCLUSIONS AND FUTURE PERSPECTIVES -- REFERENCES -- 2 Hydrogenation of Esters -- 2.1 INTRODUCTION -- 2.2 HYDROGENATION OF ALIPHATIC ESTERS -- 2.3 HYDROGENATION OF LACTONES -- 2.4 HYDROGENATION OF AROMATIC ESTERS -- 2.5 HYDROGENATION OF FURANOIC ESTERS -- 2.6 HYDROGENATION OF CHIRAL ESTERS (BASE-FREE CONDITIONS) -- 2.7 CONCLUSIONS -- REFERENCES -- 3 Synthesis of Chiral Amines Using Transaminases -- 3.1 IMPORTANCE OF CHIRAL AMINES -- 3.1.1 Challenges with Chemocatalytic Synthesis of Chiral Amines -- 3.2 TRANSAMINASES -- 3.2.1 Transaminase Mechanism -- 3.2.2 Transaminase Selectivity -- 3.3 TRANSAMINASE-CATALYZED RESOLUTION OF RACEMIC AMINES
  • 6.2 The Synthesis of Efaproxiral Utilizing a Direct Amidation Reaction -- 6.3 Direct Amidation Examples from Dr. Reddy's Laboratories -- 6.4 Direct Amidation Examples from Pfizer -- 6.5 Potential Toxicity of Boric Acid -- 6.6 Conclusions -- Acknowledgment -- References -- Chapter 7: OH Activation for Nucleophilic Substitution -- 7.1 Introduction -- 7.2 Formation of C-C Bonds from Alcohols -- 7.3 Formation of C-N Bonds from Alcohols -- References -- Chapter 8: Application of a Redox-Neutral Alcohol Amination in the Kilogram-Scale Synthesis of a GlyT1 Inhibitor -- 8.1 Introduction -- 8.2 Background and Initial Synthetic Work -- 8.3 First-Generation Synthesis of 10 -- 8.4 First Application of IR Chemistry and Initial Process Development Efforts -- 8.5 Process Optimization of the Amination Reaction -- 8.6 Mechanistic Discussion -- 8.7 Iridium Control -- 8.8 Final Comments -- Acknowledgments -- References -- Chapter 9: Olefin Metathesis: From Academic Concepts to Commercial Catalysts -- 9.1 Introduction -- 9.2 Recovery and Reuse of Ru-Based Metathesis Catalysts: The Academics' View -- 9.3 Application of Ruthenium Metathesis Catalysts in Water -- 9.4 Summary and Outlook -- Acknowledgments -- References -- Chapter 10: Challenge and Opportunity in Scaling-up Metathesis Reaction: Synthesis of Ciluprevir (Biln 2061) -- 10.1 Introduction -- 10.2 Synthesis of Ciluprevir (Biln 2061) and Critical Challenges -- 10.3 Preparations of Building Blocks -- 10.4 The First Generation Ciluprevir (Biln 2061) Process -- 10.5 Challenges in Scaling Up The RCM Reaction -- 10.6 Development of a Practical and Scalable RCM Process -- 10.7 The Second Generation Ciluprevir (Biln 2061) Process -- 10.8 Conclusion -- References -- Chapter 11: C-H Activation of Heteroaromatics -- 11.1 Introduction -- 11.2 Direct Arylation -- 11.3 Direct Alkenylation -- 11.4 Direct Alkynylation
  • Intro -- Title Page -- Copyright -- Foreword -- Preface -- Contributors -- Abbreviations -- Chapter 1: Catalytic Reduction of Amides Avoiding Lialh4 or B2H6 -- 1.1 Introduction -- 1.2 Amides -- 1.3 Importance of Amide Reductions in Pharmaceutical Synthesis -- 1.4 Heterogeneous Amide Hydrogenation -- 1.5 Homogeneous Amide Hydrogenation -- 1.6 Hydrosilation -- 1.7 Conclusions and Future Perspectives -- References -- Chapter 2: Hydrogenation of Esters -- 2.1 Introduction -- 2.2 Hydrogenation of Aliphatic Esters -- 2.3 Hydrogenation of Lactones -- 2.4 Hydrogenation of Aromatic Esters -- 2.5 Hydrogenation of Furanoic Esters -- 2.6 Hydrogenation of Chiral Esters (Base-Free Conditions) -- 2.7 Conclusions -- References -- Chapter 3: Synthesis of Chiral Amines Using Transaminases -- 3.1 Importance of Chiral Amines -- 3.2 Transaminases -- 3.3 Transaminase-Catalyzed Resolution of Racemic Amines -- 3.4 Transaminase-Catalyzed Asymmetric Synthesis of Amines -- 3.5 Conclusions -- References -- Chapter 4: Development of a Sitagliptin Transaminase -- 4.1 Introduction -- 4.2 Creating Activity -- 4.3 Transaminase Evolution -- 4.4 Process Optimization -- 4.5 A General Amination Methodology -- 4.6 Conclusion and Outlook -- 4.7 Procedures -- References -- Chapter 5: Direct Amide Formation Avoiding Poor Atom Economy Reagents -- 5.1 Introduction -- 5.2 Mechanism for Boronic and Boric Acid Catalysis -- 5.3 Boric Acid-Based Catalysis -- 5.4 Boronic Acid-Based Catalysis -- 5.5 Triazine-Based Reagents -- 5.6 Titanium(IV)-Based Reagents -- 5.7 Antimony-Based Reagents -- 5.8 Heterogeneous Catalysts and Microwave-Assisted Amide Synthesis -- 5.9 Summary and Future Directions -- References -- Chapter 6: Industrial Applications of Boric Acid and Boronic Acid-Catalyzed Direct Amidation Reactions -- 6.1 Introduction
  • 11.5 Direct Alkylation -- 11.6 Conclusion -- References -- Chapter 12: The Discovery of a New Pd/Cu Catalytic System for C-H Arylation and Its Applications in a Pharmaceutical Process -- 12.1 Introduction -- 12.2 Development of Initial Process for the Agonist of S1P1 -- 12.3 Development of C-H Arylation for the Synthesis of AMG 369 -- 12.4 Conclusion -- References -- Chapter 13: Diarylprolinol Silyl Ethers: Development and Application as Organocatalysts -- 13.1 Introduction and Background -- 13.2 Enamine Intermediate -- 13.3 Iminium ion Intermediate -- 13.4 Formal C-H Insertion -- 13.5 Reactions in the Presence of Water -- 13.6 Synthesis of Biologically Active Molecules -- 13.7 Conclusion -- References -- Chapter 14: Organocatalysis for Asymmetric Synthesis: From Lab to Factory -- 14.1 Introduction -- 14.2 Preparation of Telcagepant, an Application of Iminium Organocatalysis -- 14.3 Preparation of MK-8613, Application of Asymmetric Michael Addition Catalyzed by Desmethyl Quinidine -- 14.4 Conclusions -- Acknowledgments -- References -- Chapter 15: Catalytic Variants of Phosphine Oxide-Mediated Organic Transformations -- 15.1 General Introduction -- 15.2 Wittig Chemistry -- 15.3 Aza-Wittig Chemistry -- 15.4 Mitsunobu Chemistry -- 15.5 Appel Halogenations -- 15.6 Conclusions -- References -- Chapter 16: Formation of C-C Bonds Via Catalytic Hydrogenation and Transfer Hydrogenation -- 16.1 Introduction: Minimizing Preactivation for Synthetic Efficiency -- 16.2 Carbonyl and Imine Vinylation -- 16.3 Carbonyl Allylation and Propargylation -- 16.4 Aldol, Mannich, and Related Processes -- 16.5 Future Directions -- Acknowledgments -- References -- Index