催化学报

催化学报 ›› 2007, Vol. 28 ›› Issue (5): 469-473.

• 研究论文 • 上一篇    下一篇

环糊精手性微反应器中苯乙烯的不对称环氧化反应

肖自胜,兰支利,尹笃林,刘芳,李传华   

  1. 湖南师范大学精细催化合成研究所, 湖南长沙 410081
  • 收稿日期:2007-05-25 出版日期:2007-05-25 发布日期:2011-04-28

Asymmetric Epoxidation of Styrene in Chiral Microreactor of Cyclodextrin

XIAO Zisheng, LAN Zhili*, YIN Dulin, LIU Fang, LI Chuanhua   

  1. Institute of Fine Catalysis and Synthesis, Hunan Normal University, Changsha 410081, Hunan, China
  • Received:2007-05-25 Online:2007-05-25 Published:2011-04-28

PDF

1173

被引次数

37

摘要： 研究了酮与环糊精手性协同催化作用下,用非手性酮与过氧硫酸氢钾(商品名Oxone)原位产生的二氧杂环丙烷实现了对包合在环糊精手性微反应器中苯乙烯的不对称环氧化反应,考察了α-环糊精、β-环糊精、γ-环糊精与不同的酮协同催化反应效果,并对协同催化反应机理进行了探讨. 结果表明, β-环糊精和甲基异丁基酮(MIBK)及Oxone原位形成的二氧杂环丙烷具有较好的协同催化作用; MIBK用量、碳酸氢钠用量、反应时间和温度等因素对反应产物的收率和对映体选择性有一定的影响. 在优化条件下,环氧苯乙烷的ee值可达46%.

关键词: 苯乙烯, 环糊精, 包合物, 二氧杂环丙烷, 环氧化, 协同催化, 环氧苯乙烷

Abstract: The asymmetric epoxidation of styrene included by cyclodextrins with dioxirane produced in situ from ketones and potassium peroxymonosulfate (Oxone) was achieved. The effects of different cyclodextrins and ketones on the epoxidation of styrene were investigated, and the possible mechanism for the synergistic catalysis of cyclodextrins and ketones was suggested. The results indicated that β-cyclodextrin had good ability of chiral recognition to dioxirane that was generated in situ from methyl isobutyl ketone (MIBK) and Oxone. Various factors, such as molar ratio of MIBK to cyclodextrin inclusion complex, NaHCO3 amount, reaction time, and reaction temperature, that affected the enantiometric excess of the reaction products were examined, and the maximum enantiometric excess of1,2-epoxyethylbenzene was up to 46% under the optimal reaction conditions.

Key words: styrene, cyclodextrin, inclusion complex, dioxirane, epoxidation, synergistic catalysis, epoxyethylbenzene