手性胺膦配体氧化动力学拆分消旋亚砜  

Oxidative Kinetic Resolution of Racemic Sulfoxides with Chiral Aminophosphine Ligands

作　　者：李奇[1] 李岩云[1] 董振荣[1] 高景星[1] 

机构地区：[1]厦门大学化学化工学院,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,福建厦门361005

出　　处：《厦门大学学报（自然科学版）》2012年第6期1030-1035,共6页Journal of Xiamen University：Natural Science

基　　金：国家自然科学基金项目(20423002,20923004,21173176);厦门大学固体表面物理化学国家重点实验室项目

摘　　要：利用自行设计合成的手性多齿胺膦配体L1～L8,分别与钌、铱、铁、钛和钒等金属络合物原位组合形成催化体系,用于消旋亚砜的氧化动力学拆分反应.结果表明,手性四齿胺膦配体L8与VO(acac)2组合的体系表现出较好的活性和中等程度的对映选择性.进而研究了温度、时间和溶剂对反应的影响.以三氯甲烷作溶剂,双氧水为氧化剂,在0.01mmol催化剂用量下,-10℃时,消旋苯甲亚砜氧化动力学拆分的对映选择性达到54%ee.这项研究是手性胺膦配体在消旋亚砜动力学拆分反应中的首次应用.The catalyst systems generated in situ from chiral aminophophine ligands L1-L8 and ruthenium,iridium,iron,titanium or vanadium complexes were used for the oxidative kinetic resolution of phenyl methyl sulfoxide. The chiral diaminodiphosphine ligand L8 exhibited good activity and moderate enantioselectivity. The effects of reaction temperature, time and solvent on the oxidative ki- netic resolution were further investigated. Using H202 as oxidant,the oxidative kinetic resolution of racemic phenyl methyl sulfoxide catalyzed by 0.01 mmol L8/VO（acac）2 proceeded smoothly in CHCl3 ,obtaining （R）-sulfoxide with 54% ee at --10℃ for 16 h. Fur- thermore,it was shown that the oxidative kinetic resolution of the raeemic sulfoxides carried out in CHCl3 gave better enantioselectiv- ities than those in CH2 Cl2.

关 键 词：手性胺膦配体 钒络合物 动力学拆分 手性亚砜 

分 类 号：O643.32[理学—物理化学]