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

PETER J. DUNN, PhD, is Global Green Chemistry Lead for Pfizer. Dr. Dunn has played a key role in the development of commercial processes to make several drugs, including Viagra(t), Emselex(t), Revatio(t), and Sampatrilat. K. K. (MIMI) HII, PhD, holds a Readership in Catalysis in the Department of Chemistry at Imperial College London. Her research focuses on the development of sustainable catalytic processes for organic synthesis. MICHAEL J. KRISCHE, PhD, is Director of the Center for Green Chemistry and Catalysis and Robert A. Welch Chair in Science at The University of Texas at Austin. He is the recipient of the Tetrahedron Young Investigator Award, Humboldt Prize, Presidential Green Chemistry Challenge Award, and ACS Elias J. Corey Award. MICHAEL T. WILLIAMS, PhD, is an independent consultant. Previously, he was an executive director at Pfizer and played a key role in the development and commercialization of many drugs, including Zoloft(t), Viagra(t), and Relpax(t).

Foreword vii Preface ix Contributors xi Abbreviations xiii 1 Catalytic Reduction of Amides Avoiding LiAlH4 or B2H6 1 Deborah L. Dodds and David J. Cole-Hamilton 2 Hydrogenation of Esters 37 Lionel A. Saudan 3 Synthesis of Chiral Amines Using Transaminases 63 Nicholas J. Turner and Matthew D. Truppo 4 Development of a Sitagliptin Transaminase 75 Jacob M. Janey 5 Direct Amide Formation Avoiding Poor Atom Economy Reagents 89 Benjamin M. Monks and Andrew Whiting 6 Industrial Applications of Boric Acid and Boronic Acid-Catalyzed Direct Amidation Reactions 111 Joanne E. Anderson, Jannine Cobb, Roman Davis, Peter J. Dunn, Russ N. Fitzgerald, and Alan J. Pettman 7 OH Activation for Nucleophilic Substitution 121 Jonathan M.J. Williams 8 Application of a Redox-Neutral Alcohol Amination in the Kilogram-Scale Synthesis of a GlyT1 Inhibitor 139 Martin A. Berliner 9 Olefin Metathesis: From Academic Concepts to Commercial Catalysts 163 Justyna Czaban, Christian Torborg, and Karol Grela 10 Challenge and Opportunity in Scaling-up Metathesis Reaction: Synthesis of Ciluprevir (BILN 2061) 215 Nathan Yee, Xudong Wei, and Chris Senanayake 11 C--H Activation of Heteroaromatics 233 Koji Hirano and Masahiro Miura 12 The Discovery of a New Pd/Cu Catalytic System for C--H Arylation and Its Applications in a Pharmaceutical Process 269 Jinkun Huang, Xiang Wang, and Johann Chan 13 Diarylprolinol Silyl Ethers: Development and Application as Organocatalysts 287 Hiroaki Gotoh and Yujiro Hayashi 14 Organocatalysis for Asymmetric Synthesis: From Lab to Factory 317 Feng Xu 15 Catalytic Variants of Phosphine Oxide-Mediated Organic Transformations 339 Stephen P. Marsden 16 Formation of C--C Bonds Via Catalytic Hydrogenation and Transfer Hydrogenation 363 Joseph Moran and Michael J. Krische Index 409