Research Progress of Hydrolytic Kinetic Resolution of Epichlorohydrin Catalyzed by Salen Metal Complexes

doi:10.12422/j.issn.1006-396X.2023.04.008

Abstract

Abstract:

Chiral epichlorohydrin is obtained by kinetic resolution of racemic epichlorohydrin through hydrolysis. Chiral epichlorohydrin is a valuable intermediate which is widely used in the synthesis of medicine and material. Salen refers to a base formed by the condensation of two identical aldehyde molecules and a diamine molecule, and the complex formed by its combination with metals is called Salen metal complex, which is often used in the synthesis of chiral epichlorohydrin. In this paper, the development of Salen metal complex catalysts and their application in chiral epichlorohydrin synthesis are reviewed. At the same time, the deactivation mechanism of catalyst in the process of hydrolytic kinetic resolution was investigated and the application prospect of synthesis of chiral epichlorohydrin using Salen metal complex catalysts was prospected.

Key words: Chiral epichlorohydrin, Salen metal complex, Hydrolytic kinetic resolution, Enantiomer

摘要：

环氧氯丙烷通过水解动力学拆分可得到手性环氧氯丙烷。手性环氧氯丙烷是具有很高价值的中间体，被广泛应用于医药、材料等领域。Salen是指两个相同的醛分子和一个二胺分子缩合生成的碱，其与金属化合形成的配合物被称为Salen金属配合物，常用于手性环氧氯丙烷的合成。综述了近年来Salen金属配合物催化剂的发展历程及其用于手性环氧氯丙烷合成的研究进展，探究了水解动力学拆分过程中催化剂的失活机理，对以Salen金属配合物为催化剂合成的手性环氧氯丙烷的应用进行了展望。

关键词: 手性环氧氯丙烷, Salen金属配合物, 水解动力学拆分, 对映体

CLC Number:

TQ013.2

Na Liu, Guangmin Liang, Jiuyu Ji, Kun Zhou, Genxiang Luo, Wei Li. Research Progress of Hydrolytic Kinetic Resolution of Epichlorohydrin Catalyzed by Salen Metal Complexes[J]. Journal of Petrochemical Universities, 2023, 36(4): 53-62.

刘娜, 梁光敏, 季久玉, 周坤, 罗根祥, 李微. Salen金属配合物水解动力学拆分环氧氯丙烷研究进展[J]. 石油化工高等学校学报, 2023, 36(4): 53-62.

Figures/Tables 21

Fig.1 Structure of catalyst 1

Fig.2 Structure of catalyst 2

Fig.3 Structure of catalyst 3 and its catalytic hydrolysis kinetic resolution of epichlorohydrin

Fig.4 Structure of catalyst 4 and its catalytic hydrolysis kinetic resolution of epichlorohydrin

Fig.5 Structure of catalyst 5

Fig.6 Structure of catalyst 6 and its catalytic hydrolysis kinetic resolution of epichlorohydrin

Fig.7 Synthesis route of catalyst 7

Fig.8 Structure of catalyst 8 and its catalytic hydrolysis kinetic resolution of epichlorohydrin

Fig.9 Structure of catalyst 9 and its catalytic hydrolysis kinetic resolution of epichlorohydrin

Fig.10 Structure of catalyst 10 and its catalytic hydrolysis kinetic resolution of epichlorohydrin

Fig.11 Structure of catalyst 11 and its catalytic hydrolysis kinetic resolution of epichlorohydrin

Fig.12 Structure of catalyst 12 and its catalytic hydrolysis kinetic resolution of epichlorohydrin

Fig.13 Structure of catalyst 13 and its catalytic hydrolysis kinetic resolution of epichlorohydrin

Fig.14 Structure of catalyst 14 and its catalytic hydrolysis kinetic resolution of epichlorohydrin

Fig.15 Hydrolytic kinetic resolution of epichlorohydrin by catalyst 15

Fig.16 Structure of catalyst 16 and its catalytic hydrolysis kinetic resolution of epichlorohydrin

Fig.17 Structure of catalyst 17 and its catalytic hydrolysis kinetic resolution of epichlorohydrin

Fig.18 Structure of catalyst 18 and its catalytic hydrolysis kinetic resolution of epichlorohydrin

Fig.19 HKR of terminal epoxides catalyzed by Co(Ⅲ)?Salen bimetallic complex

Fig.20 Catalyst Co-X(X≠OH) dominant HKR reactions of terminal epoxide

Fig.21 Mechanism of counterion activity on Co?Salen catalyst

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