同手性二聚体钴-水杨醛络合物在末端外消旋环氧化物水解动力学拆分中催化活性的提高。

Improved catalytic activity of homochiral dimeric cobalt-salen complex in hydrolytic kinetic resolution of terminal racemic epoxides.

作者信息

Kureshy Rukhsana I, Singh Surendra, Khan Noor-Ul H, Abdi Sayed H R, Ahmad Irshad, Bhatt Achyut, Jasra Raksh V

机构信息

Silicates and Catalysis Discipline, Central Salt and Marine Chemicals Research Institute (CSMCRI), Bhavnagar, India.

出版信息

Chirality. 2005 Nov;17(9):590-4. doi: 10.1002/chir.20196.

DOI:10.1002/chir.20196

PMID:16200537

Abstract

Enantiomerically pure epoxides (99%, ee) and diols (98%, ee) from racemic epichlorohydrin, 1,2-epoxypropane, 1,2-epoxyhexane, 1,2-epoxyoctane, and 1,2-epoxydodecane were obtained in 2-12 h by hydrolytic kinetic resolution (HKR) using the recyclable dimeric homochiral Co(III)-salen complex 1' (0.2 mol %) derived from 5,5-(2',2'-dimethylpropane)-di-[(R,R)-{N-(3-tert-butylsalicylidine)-N'-(3',5'-di-tert-butylsalicylidine)}-1,2-cyclohexanediamine] with cobalt(II) acetate. Unlike its monomeric version, the catalyst could be recycled several times without loss in performance. The use of BF(4) as counter ion in HKR reactions was also investigated.

摘要

通过水解动力学拆分（HKR），使用由5,5-(2',2'-二甲基丙烷)-二-[(R,R)-{N-(3-叔丁基水杨醛)-N'-(3',5'-二叔丁基水杨醛)}-1,2-环己二胺]与醋酸钴衍生的可循环二聚体同手性Co(III)-salen配合物1'（0.2 mol%），在2至12小时内从外消旋环氧氯丙烷、1,2-环氧丙烷、1,2-环氧己烷、1,2-环氧辛烷和1,2-环氧十二烷中获得对映体纯的环氧化物（99%，ee）和二醇（98%，ee）。与单体形式不同，该催化剂可以循环使用多次而性能不损失。还研究了在HKR反应中使用BF(4)作为抗衡离子的情况。