高等学校化学学报 ›› 2019, Vol. 40 ›› Issue (7): 1488-1494.doi: 10.7503/cjcu20190011

• 物理化学 • 上一篇    下一篇

胺基功能化ZPS-PVPA固载手性Mn(salen)的合成及不对称催化烯烃环氧化

邹晓川, 王跃, 王存, 胡世文, 石开云()   

  1. 重庆第二师范学院生物与化学工程学院, 重庆 400067
  • 收稿日期:2019-01-04 出版日期:2019-06-28 发布日期:2019-07-09
  • 作者简介:

    石开云, 男, 博士, 副教授, 主要从事药物分子设计合成及天然物质提取分离方面的研究. E-mail: shiky@cque.edu.cn

  • 基金资助:
    重庆市自然科学基金(批准号: cstc2018jcyjAX0110)、 重庆市教育委员会科学技术研究项目(批准号: KJ201801607, KJQN201801602)、 重庆第二师范学院绿色合成及分析检测重点实验室项目(批准号: 2016kjpt08)、 重庆第二师范学院药物化学研究所项目(批准号: KYC-yjs02-2017004)和重庆第二师范学院青年人才项目(批准号: 160921zt)资助.

Synthesis of Amine Functionalized ZPS-PVPA Supported Chiral Mn(salen) and Asymmetric Catalytic Olefin Epoxidation

ZOU Xiaochuan, WANG Yue, WANG Cun, HU Shiwen, SHI Kaiyun*()   

  1. Department of Biological & Chemical Engineering, Chongqing University of Education, Chongqing 400067, China
  • Received:2019-01-04 Online:2019-06-28 Published:2019-07-09
  • Contact: SHI Kaiyun E-mail:shiky@cque.edu.cn
  • Supported by:
    † Supported by the the Natural Science Foundation of Chongqing, China(No.cstc2018jcyjAX0110), the Science and Technology Research Program of Chongqing Municipal Education Commission, China(Nos.KJ201801607, KJQN201801602), the Key Laboratory for Green Chemical Technology of Chongqing University of Education, China(No.2016kjpt08), the Institute of Medicinal Chemistry of Chongqing University of Education, China(No.KYC-yjs02-2017004) and the Youth Talent Project of Chongqing University of Education, China(No.160921zt).

摘要:

以聚(苯乙烯-苯乙烯基膦酸)-磷酸氢锆(ZPS-PVPA)为催化剂载体, 通过3-氨丙基三甲氧基硅烷对其中无机磷酸氢锆的羟基进行修饰, 再与均相手性Mn(salen)催化剂进行轴向配位固载, 实现了手性均相催化剂的非均相化. 催化剂的表征结果证实制得了非均相催化剂. 随后, 考察了该非均相催化剂对α-甲基苯乙烯、 苯乙烯以及茚不对称环氧化反应的催化性能. 结果表明, 以间氯过氧苯甲酸(m-CPBA)为氧化剂, 在 0 ℃反应 3 h, 催化剂用量为 0.03 mmol, 在轴向配体 N-甲基吗啉氮氧化物(NMO)的参与下, 催化剂能高效催化α-甲基苯乙烯的不对称环氧化, 反应的对映选择性(e. e.值)可达 91.5%, 转化率为 99%. 此外, 以茚为底物考察了催化剂的循环使用性能, 结果表明, 催化剂重复使用10次后, 反应的e. e.值(>90%)远高于在相同条件下均相Mn(salen)催化剂催化茚反应的e. e.值(65%).

关键词: 聚(苯乙烯-苯乙烯基膦酸)-磷酸氢锆, 3-氨丙基三甲氧基硅烷, 手性Mn(salen)催化剂, 不对称环氧化反应

Abstract:

Using zirconium poly(styrene-phenylvinyl-phosphonate)-phosphate(ZPS-PVPA) as a catalyst carrier, the hydroxyl group in the inorganic zirconium hydrogen phosphate was modified by 3-aminopropyltrimethoxysilane. Then, the chiral Mn(salen) was axially immobilized onto amine functionalized ZPS-PVPA. The immobilized catalyst were characterized by FTIR, DR UV-Vis, AAS, SEM, TEM, XPS, X-ray and EDS. The successful preparation of heterogeneous catalysts was confirmed. Subsequently, the catalytic performance of the supported catalyst for α-methylstyrene, styrene and indene was examined in detail. The results showed that the reaction was carried out at 0 ℃ for 3 h, the amount of catalyst was 0.03 mmol, the e. e. value was 91.5% with a 99% conversion when α-methylstyrene was investigated using m-chloroperoxybenzoic acid as oxidant and in the present of the axial ligand N-methylmorpholine nitrogen oxide(NMO). In addition, the recycling performance of the catalyst was examined using indene as a substrate. After 10 times of repeated use of the catalyst, the e. e. values(>90%)are significantly better than those achieved under a homogeneous counterparts(e. e. 65%).

Key words: Zirconium poly(styrene-phenylvinyl-phosphonate)-phosphate, 3-Aminopropyltrimethoxysilane, Chiral Mn(salen) catalyst, Asymmetric epoxidation

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