Modern Tools for the Synthesis of Complex Bioactive Molecules

JANINE COSSY graduated from the University of Reims working under the supervision of Prof. Jean-Pierre Pète. After a postdoctoral stay with Prof. Barry Trost (1980-1982) at the University of Wisconsin, she returned to Reims where she became Director of Research of the CNRS in 1990. The same year, she moved to Paris to become Professor of Organic Chemistry at the Ecole Supérieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI ParisTech). She has published over 380 articles and filed thirteen patents in the field of synthetic organic chemistry and natural product synthesis. She is Associate Editor at Organic Letters since 2005. STELLIOS ARSENIYADIS was born in Greece in 1975. He studied chemistry at the Université Paris XI and received his PhD in 2002 from the Université Louis Pasteur (Strasbourg, France) working under the guidance of Dr. Charles Mioskowski. In 2001, he joined Rhodia ChiRex (Boston, USA) for an eighteen-month internship in collaboration with Prof. Stephen L. Buchwald (MIT, USA). He then spent a year as a postdoctoral fellow at Imperial College London (UK) working under the supervision of Prof. Alan C. Spivey, after which he joined Prof. K. C. Nicolaou's group at The Scripps Research Institute (La Jolla, USA) for an additional postdoc. In 2005, he was appointed by the CNRS as Chargé de Recherche in Prof. Janine Cossy's group. His research interests include the development of new synthetic tools and their application to the total synthesis of complex natural products.

FOREWORD vii

PREFACE ix

CONTRIBUTORS xi

CHAPTER 1 C–H FUNCTIONALIZATION: A NEW STRATEGY FOR THE SYNTHESIS OF BIOLOGICALLY ACTIVE NATURAL PRODUCTS 1
Sophie Rousseaux, Benoýˆt Lie´gault, and Keith Fagnou

CHAPTER 2 THE NEGISHI CROSS-COUPLING IN THE SYNTHESIS OF NATURAL PRODUCTS AND BIOACTIVE MOLECULES 33
Evelina Colacino, Jean Martinez, and Fre´de´ric Lamaty

CHAPTER 3 METAL-CATALYZED C–HETEROATOM CROSS-COUPLING REACTIONS 77
Renata Marcia de Figueiredo, Jean Marc Campagne, and Damien Prim

CHAPTER 4 GOLDEN OPPORTUNITIES IN THE SYNTHESIS OF NATURAL PRODUCTS AND BIOLOGICALLY ACTIVE COMPOUNDS 111
Fabien Gagosz

CHAPTER 5 METATHESIS-BASED SYNTHESIS OF COMPLEX BIOACTIVES 155
Jean-Alexandre Richard, Sin Yee Ng, and David Y.-K. Chen

CHAPTER 6 ENANTIOSELECTIVE ORGANOCATALYSIS: A POWERFUL TOOL FOR THE SYNTHESIS OF BIOACTIVE MOLECULES 189
Mitsuru Shoji and Yujiro Hayashi

CHAPTER 7 ASYMMETRIC PHASE-TRANSFER CATALYSIS 213
Seiji Shirakawa, Shin A. Moteki, and Keiji Maruoka

CHAPTER 8 REARRANGEMENTS IN NATURAL PRODUCT SYNTHESIS 243
Jose´ Marco-Contelles and Elena Soriano

CHAPTER 9 DOMINO REACTIONS IN THE ENANTIOSELECTIVE SYNTHESIS OF BIOACTIVE NATURAL PRODUCTS 271
Lutz F. Tietze, Scott G. Stewart, and Alexander Du¨fert

CHAPTER 10 FLUOROUS LINKER-FACILITATED SYNTHESIS OF BIOLOGICALLY INTERESTING MOLECULES 335
Wei Zhang

CHAPTER 11 THE EVOLUTION OF IMMOBILIZED REAGENTS AND THEIR APPLICATION IN FLOW CHEMISTRY FOR THE SYNTHESIS OF NATURAL PRODUCTS AND PHARMACEUTICAL COMPOUNDS 359
Rebecca M. Myers, Kimberley A. Roper, Ian R. Baxendale, and Steven V. Ley

CHAPTER 12 SYNTHETIC APPROACHES TO BIOACTIVE CARBOHYDRATES 395
Xavier Guinchard, Se´bastien Picard, and David Crich

CHAPTER 13 AMMONIUM YLIDES AS BUILDING BLOCKS FOR ALKALOID SYNTHESIS 433
Scott Bur and Albert Padwa

CHAPTER 14 PRECURSOR-DIRECTED BIOSYNTHESIS OF POLYKETIDE AND NONRIBOSOMAL PEPTIDE NATURAL PRODUCTS 485
Colin J. B. Harvey and Chaitan Khosla

CHAPTER 15 TARGET-ORIENTED AND DIVERSITY-ORIENTED ORGANIC SYNTHESIS 513
Raphae¨l Rodriguez

CHAPTER 16 DNA AS A TOOL FOR MOLECULAR DISCOVERY 539
Michael Smietana, Jean-Jacques Vasseur, Janine Cossy, and Stellios Arseniyadis

INDEX 557