Asymmetric Organometallic Catalysis - Société Chimique ：催化不对称有机金属化学公司.pdfVIP

Asymmetric Organometallic Catalysis J.-P. Genet, V. Michelet, V. Vidal Laboratoire de Synthèse Sélective Organique et Produits Naturels – UMR CNRS 7573 E.N.S.C.P. - 11 Rue P. M. Curie – 75231 PARIS Cedex 05 jean-pierre-genet@enscp.fr ; veronique-michelet@enscp.fr ; virginie-vidal@enscp.fr 1 - Introduction Asymmetric catalysis has become one of the most powerful methods to produce a single-enantiomer drug and now provides one of the most cost-effective and environmentally responsible methods for the production of a vast array of structurally diverse, enantiomerically pure compounds. Since a small amount of chiral catalyst can, in principle, produce a large amount of optically active product. Transition metal enantioselective catalysis is certainly among the most challenging and widely investigated area in modern organometallic chemistry. In 1971, H. B. Kagan and T. P. Dang discovered the Diop ligand or (2,3-O-isopropylidene)-2,3-dihydroxy-1, 4-bis (diphenylphosphino)butane[1], the first C2-symmetric diphosphane that allowed asymmetric hydrogenation of dehydroamino acids , when complexed with rhodium. The basic idea was that a suitable functionality and skeletal rigidity of the phosphine ligand would contribute to the differentiation of transition states needed to accomplish enantioselective catalysis. The rhodium (I)-DIOP catalyst was superior to monophosphines catalysts in asymmetric hydrogenation of dehydro amino acids. It is interesting to note that Pr. H. B. Kagans 1970 initial patent also includes the structure of an atropisomeric ligand, a potential candidate for asymmetric catalysis, w