【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.更多还原

【Abstract】 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 kinetic resolution were further investigated.Using H2O2 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.Furthermore,it was shown that the oxidative kinetic resolution of the racemic sulfoxides carried out in CHCl3 gave better enantioselectivities than those in CH2Cl2.更多还原