手性多齿胺膦钌配合物的设计合成和在芳香酮不对称氢化反应中的应用

Designed Synthesis of New Chiral Diaminodiphosphine Ruthenium Complexes and Their Application in Enantioselective Hydrogenation of Aromatic Ketones

简要介绍了多齿胺膦金属配合物的设计合成．这些多齿配合物显示了单齿胺或膦金属配合物所不具有的丰富结构类型和特殊催化性质．合成和表征了含有结构类似的双亚胺双膦钌配合物（Ｒ，Ｒ）－３和双胺双膦钌配合物（Ｒ，Ｒ）－４．配合物（Ｒ，Ｒ）－４可作为多种芳香酮不对称氢化的手性催化剂，其光学收率最高达９７％．讨论了钌配合物的催化作用机理．

The designed synthesis of new metal complexes with C 2 symmetric diimino or diamino diphosphine ligands has been briefly reviewed. These metal complexes display some interesting structural, chemical and catalytic properties that are not observed in other phosphine or amine complexes. New ruthenium(Ⅱ) complex with structurally similar N,N′ bis[ o (diphenylphosphino)benzylidene]cyclohexane 1,2 diamine and N,N′ bis[ o (diphenylphosphino)benzylidene]cyclohexane 1,2 diamine ligands were synthesized and their strucutres were determined. The trans RuCl 2 complex with C 2 symmetric diamine/diphosphine tetradentate ligands has been found to be an effective catalyst precursor for the asymmetric transfer hydrogenation of aromatic ketones with up to 97% enantiomeric excess. The mechanism of asymmetric transfer reduction of ketones has been also discussed.