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

作　　者：高景星[1] 许翩翩[1] 黄培强[1] 万惠霖[1] 蔡启瑞[1] 碇屋隆雄 野依良治 

机构地区：[1]厦门大学化学系物理化学研究所固体表面物理化学国家重点实验室 [2]日本科学技术振兴事业团

出　　处：《分子催化》1997年第6期413-416,共4页Journal of Molecular Catalysis(China)

基　　金：国家自然科学基金

摘　　要：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.

关 键 词：手性胺膦配体 不对称氢化 不对称催化 钌配合物 

分 类 号：O643.36[理学—物理化学] O621.254.2[理学—化学]