手性胺膦配体在不对称催化中的应用  

Chiral diaminodiphosphine ligands in asymmetric catalysis

作　　者：李岩云[1] 董振荣[1] 张娟妮 高景星[1] 

机构地区：[1]固体表面物理化学国家重点实验室醇醚酯化工清洁生产国家工程实验室厦门大学化学化工学院化学系,厦门361005

出　　处：《中国科学：化学》2011年第4期654-662,共9页SCIENTIA SINICA Chimica

基　　金：国家自然科学基金(20423002;20703034)资助

摘　　要：利用邻二苯基膦苯甲醛分别与多种手性二胺的缩合反应,设计合成了一系列新型手性四齿胺膦配体.这类多齿胺膦配体含有两个"软"的磷原子和两个"硬"的氮原子,具有丰富的配位化学性能和优秀的不对称诱导能力.本文综述了手性胺膦金属络合物催化剂在不对称转移氢化反应、氧化动力学拆分反应、烯烃的不对称环氧化反应和不对称环丙烷化反应、不对称D-A反应中的应用.A series of chiral tetradentate diaminodiphosphine ligands（PNNP-type） have been synthesized and characterized.These ligands contain two＂soft＂phosphorus atoms and two＂hard＂nitrogen atoms,which display the rich coordination chemistry and easily modify the steric and electronic properties of the resulting metal complexes. Based on these polydentate mixed-P,N ligands,the chiral PNNP-Ru,PNNP-Rh and PNNP-Fe complexes were prepared and used as catalysts in the asymmetric transfer hydrogenation of aromatic ketones with up to 99% ee and even the molar ratio of ketone to catalyst up to 10000：1.The catalytic reaction mechanism of ATH will be discussed.The PNNP ligands extensively used in asymmetric epoxidation,cyclopropanation and kinetic resolution by other researchers and us are also reviewed.

关 键 词：手性胺膦配体 不对称催化 不对称转移氢化 芳香酮 

分 类 号：O643.32[理学—物理化学]