手性Salen稀土金属配合物催化外消旋环氧氯丙烷的水解动力学拆分

Hydrolytic Kinetic Resolution of Racemic Epichlorohydrin Catalyzedby Chiral Rare Earth Salen Complexes

将原位生成的Salen稀土金属催化剂直接用于催化消旋环氧氯丙烷的水解动力学拆分,考察了温度、金属中心、反应时间、催化剂负载量、水的用量对该拆分反应的影响。结果表明稀土金属Salen配合物是催化消旋环氧氯丙烷水解动力学拆分的高效高选择性催化剂。最佳条件为温度为0～5℃,催化剂为0.3 mol%的Salen Yb(III)配合物,反应时间为18 h,水的用量为0.55当量,此时(S)-环氧氯丙烷的产率为44%,ee值为99%。该一锅法操作简单,易于工业化生产。

In this paper, lanthanide are combined in situ with the chiral ligand, the genarated salen lanthanides comple- xes directly catalyzed the hydrolytic kinetic resolution of racemic epichlorohydrine （ ECH）, the effects of reaction temperature, metal salts center, time, loading amount of catalysts and the dosage of water on the yield were investigated. It was found experi- mentally that （S） - ECH was being generated in high yield （44%） and enantiomeric excess （99%） by hydrolytic kinetic res- olution of racemic ECH using O. 55 equiv of water in the presence of0. 3 mol% of salen Yb（III） complex for 18 hours at 0 ℃ ~ 5 ℃. This one - pot method was simple in operation, so it was more suitable for industrial production.