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化学学报
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化学学报 ›› 2011, Vol. 69 ›› Issue (14): 1681-1687. 上一篇    下一篇

研究论文

新型烷氧基修饰的手性Salen Mn(III)固载催化剂的合成及其在非功能化烯烃不对称环氧化反应中的应用

王长炜1,2，傅相锴*,1,2,3，黄静1,2   

  1. (1西南大学化学化工学院应用化学研究所 重庆 400715)
    (2重庆市应用化学市级重点实验室 重庆 400715)
    (3三峡库区生态环境教育部重点实验室 重庆 400715)
  • 投稿日期:2011-01-21 修回日期:2011-03-11 发布日期:2011-03-24
  • 通讯作者: 傅相锴 E-mail:changwei@swu.edu.cn

Synthesis and Application of New Alkoxyl-Modified Immobilized Chiral Salen Mn(III) Complexes in Asymmetric Epoxidation of Unfuntionalized Olefins

Wang Changwei1,2 Fu Xiangkai*,1,2,3 Huang Jing1,2   

  1. (1 Research Institute of Applied Chemistry, College of Chemistry and Chemical Engineering, Southwest University, Chongqing 400715)
    (2 Key Laboratory of Applied Chemistry of Chongqing Municipality, Chongqing 400715)
    (3 Key Laboratory of Eco-environments in Three Gorges Reservoir Region, Ministry of Education, Chongqing 400715)
  • Received:2011-01-21 Revised:2011-03-11 Published:2011-03-24
  • Contact: Xiang-Kai FU E-mail:changwei@swu.edu.cn

PDF

1087

被引次数

15

合成了一系列以有机聚合物-无机杂化材料聚(苯乙烯-苯乙烯基膦酸)-磷酸氢锆(ZPS-PVPA)为载体, 烷氧基为连接基团的新型固载手性Salen Mn(III)催化剂, 并运用FT-IR, UV-vis, XPS, SEM, TG, 元素分析等手段对其进行了表征. 以m-CPBA为氧化剂, 茚和α-甲基苯乙烯为底物, 考察了催化剂对非功能化烯烃不对称环氧化反应的催化性能. 结果表明, 在相同的催化反应条件下, 固载手性Salen Mn(III)催化剂3a～3f在不加轴向配体N-甲基吗啉氮氧化物(NMO)时显示出了优良的催化活性, 其转化率和ee值均比添加了轴向配体NMO时有很大的提高, 这种现象与大多数文献报道相反. 此外, 催化剂容易分离, 且回收使用10次仍能保持较好的催化活性.

关键词: 聚(苯乙烯-苯乙烯基膦酸)-磷酸氢锆, 烷氧基修饰, Salen Mn(III), 非功能化烯烃, 不对称环氧化反应

New types of supported catalysts were obtained by anchoring chiral salen Mn(III) complex on a series of alkoxyl-modified zirconium poly(styrene-phenylvinyl phosphonate)-phosphate (ZPS-PVPA) in the text. All the prepared catalysts were characterized by FT-IR, UV-vis, XPS, SEM, TG and elemental analysis. The catalytic capabilities were investigated with m-CPBA as an oxidant and with indene and α-methylstyrene as substrates for asymmetric epoxidation of unfunctionalized olefins. Contrary to most of the literatures reported, the results showed that the heterogeneous catalysts 3a～3f exhibited excellent catalytic activities, and their conversions and ee values increased remarkably in the absent of N-methyl- morpholine N-oxide (NMO) under the same catalytic conditions. Futhermore, these catalysts were easily separated and reused ten times without significant loss of activities.

Key words: zirconium poly(styrene-phenylvinyl phosphonate)-phosphate, alkoxyl-modified, Salen Mn(III), unfunctionalized olefins, asymmetric epoxidation