可调苯氧基修饰的聚(苯乙烯-苯乙烯基膦酸)-磷酸氢锆固载手性MnⅢ(Salen)高效催化烯烃环氧化

doi:10.1016/S1872-2067(14)60064-4

催化学报 ›› 2014, Vol. 35 ›› Issue (9): 1446-1455.DOI: 10.1016/S1872-2067(14)60064-4

可调苯氧基修饰的聚(苯乙烯-苯乙烯基膦酸)-磷酸氢锆固载手性Mn^Ⅲ(Salen)高效催化烯烃环氧化

邹晓川^a,b, 石开云^a, 王存^a

a 重庆第二师范学院生物与化学工程系, 重庆400067;
b 西南大学应用化学研究所, 重庆市应用化学重点实验室, 三峡库区生态环境教育部重点实验室, 重庆400715

收稿日期:2014-01-30 修回日期:2014-02-21 出版日期:2014-08-19 发布日期:2014-08-22
通讯作者: 邹晓川
基金资助:
重庆市基础与前沿研究计划（cstc2013jcyjA50013）；重庆市教委科学技术研究项目（KJ131504）；重庆高校创新团队建设计划（KJTD201325）.

Chiral Mn^Ⅲ(Salen) supported on tunable phenoxyl group modified zirconium poly (styrene-phenylvinylphosphonate)-phosphate as an efficient catalyst for epoxidation of unfunctionalized olefins

Xiaochuan Zou^a,b, Kaiyun Shi^a, Cun Wang^a

a Department of Biological and Chemical Engineering, Chongqing University of Education, Chongqing 400067, China;
b College of Chemistry and Chemical Engineering, Research Institute of Applied Chemistry, The Key Laboratory of Applied Chemistry of Chongqing Municipality, The Key Laboratory of Eco-environments in Three Gorges Reservoir Region Ministry of Education, Southwest University, Chongqing 400715, China

Received:2014-01-30 Revised:2014-02-21 Online:2014-08-19 Published:2014-08-22
Supported by:
This work was supported by the Basic and Frontier Research Project of Chongqing (cstc2013jcyjA50013), Scientific and Technological Research Program of Chongqing Municipal Education Commission (KJ131504), and the Innovation Team Building at Institutions of Higher Education in Chongqing (KJTD201325).

摘要/Abstract

摘要：

使用不同空间位阻的苯氧链接手臂修饰的聚（苯乙烯基-苯乙烯膦酸）-磷酸氢锆轴向固载手性Mn^Ⅲ（Salen）催化剂（Cat₁-Cat₃），随后在间氯过氧苯甲酸（m-CPBA）为氧化剂的体系中考察了固载催化剂的催化性能. 同时，在相同氧化体系下测试了一系列均相催化剂类似物（Cat₄-Cat₆）. 结果表明，在非均相条件下，可调变苯氧链接手臂的邻位取代基对催化剂活性起着重要作用，环氧化产物的对映选择性随着取代基位阻的增加而增大，但产物转化率有一定程度下降. 此外，非均相催化剂即使在没有轴向助剂的参与下（通常需要添加，为了增大催化活性）仍然表现出非常高的催化活性，尤其对α-甲基苯乙烯反应，其对映选择性从6.8%增加到76.8%，转化率从19.8%上升到90.7%. 制备的非均相催化剂11次的循环使用实验表明，在前5次使用后催化剂活性与对映选择性没有明显变化.

关键词: 聚(苯乙烯基-苯乙烯膦酸)-磷酸氢锆, 手性Jacobsen催化剂, 可调变苯氧链接基团, 不对称非均相环氧化

Abstract:

We have developed a series of chiral Mn^Ⅲ(Salen) (chiral Jacobsen's catalyst) catalysts that were axially supported onto zirconium poly(styrene-phenylvinylphosphonate)-phosphate through tunable phenoxyl linkers of varying steric hindrance, and evaluated their performance as catalysts (Cat₁-Cat₃) for the epoxidation of unfunctionalized olefins using m-chloroperbenzoic acid as an oxidant. The corresponding non-supported analogues (Cat₄-Cat₆) were also prepared and tested under similar conditions. The results demonstrated that the incorporation of substituents at the ortho-positions of the tunable phenoxyl linkers had a critical effect on the catalytic activity. Furthermore, the enantioselectivity increased as the steric hindrance imposed by the linker increased, although this also led to a decrease in the conversions under the same reaction conditions, especially for heterogeneous epoxidation. The heterogeneous system also displayed high ee values and conversions in the absence of the axial additive N-methylmorpholine N-oxide, which is commonly required to improve the catalytic activity of epoxidation reactions, especially for the epoxidation of α-methylstyrene. The reusability of the catalyst was also evaluated over 11 catalytic cycles, with no significant reduction observed in the catalytic activity or enantioselectivity after five runs.

Key words: Zirconium, Poly(styrene-phenylvinylphosphonate)-phosphate, Chiral Jacobsen’s Catalyst, Tunable phenoxyl linker groups, Asymmetric Epoxidation of Alkenes

邹晓川, 石开云, 王存. 可调苯氧基修饰的聚(苯乙烯-苯乙烯基膦酸)-磷酸氢锆固载手性Mn^Ⅲ(Salen)高效催化烯烃环氧化[J]. 催化学报, 2014, 35(9): 1446-1455.

Xiaochuan Zou, Kaiyun Shi, Cun Wang. Chiral Mn^Ⅲ(Salen) supported on tunable phenoxyl group modified zirconium poly (styrene-phenylvinylphosphonate)-phosphate as an efficient catalyst for epoxidation of unfunctionalized olefins[J]. Chinese Journal of Catalysis, 2014, 35(9): 1446-1455.

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可调苯氧基修饰的聚(苯乙烯-苯乙烯基膦酸)-磷酸氢锆固载手性Mn^Ⅲ(Salen)高效催化烯烃环氧化

Chiral Mn^Ⅲ(Salen) supported on tunable phenoxyl group modified zirconium poly (styrene-phenylvinylphosphonate)-phosphate as an efficient catalyst for epoxidation of unfunctionalized olefins

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Chiral MnⅢ(Salen) supported on tunable phenoxyl group modified zirconium poly (styrene-phenylvinylphosphonate)-phosphate as an efficient catalyst for epoxidation of unfunctionalized olefins

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Chiral Mn^Ⅲ(Salen) supported on tunable phenoxyl group modified zirconium poly (styrene-phenylvinylphosphonate)-phosphate as an efficient catalyst for epoxidation of unfunctionalized olefins