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有机化学
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有机化学 ›› 2007, Vol. 27 ›› Issue (07): 862-865. 上一篇    下一篇

研究论文

手性β-氨基醇催化α,β-不饱和酮的不对称环氧化反应

柳文敏*，王巧峰，张生勇*   

  1. (a南阳师范学院化学与制药工程学院 南阳 473061)
    (b第四军医大学药学系化学教研室 西安 710032)
  • 收稿日期:2006-10-08 修回日期:1900-01-01 发布日期:2007-06-30
  • 通讯作者: 柳文敏*，张生勇*

Asymmetric Epoxidation of α,β-Enones Catalyzed by Chiral β-Aminoalcohols

LIU Wen-Min*,WANG Qiao-Feng,ZHANG Sheng-Yong*   

  1. (a College of Chemistry and Pharmaceutical Engineering, Nanyang Normal University, Nan-yang 473061)
    (b Department of Chemistry, School of Pharmacy, the Fourth Military Medical University, Xi'an 710032)
  • Received:2006-10-08 Revised:1900-01-01 Published:2007-06-30
  • Contact: LIU Wen-Min*,ZHANG Sheng-Yong*

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将以烯烃为原料通过Sharpless不对称双羟化等多步反应合成的8种手性β-氨基醇, 作为有机小分子催化剂, 用于催化α,β-不饱和酮的不对称环氧化反应．考察了影响对映选择性的催化剂结构、催化剂用量、氧化剂种类、溶剂、反应温度等因素．结果表明, 当催化剂用量为30 mol%、氧化剂为TBHP(叔丁基过氧化氢)、正己烷溶剂、在室温下、以(1S,2R)-(＋)-1,2-二苯基-2-甲氨基乙醇(3)作催化剂时, 所得环氧化物的对映体过量最高为70% ee, 产率最高为84%.

关键词: 不对称环氧化, 手性β-氨基醇, α,β-不饱和酮, 不对称催化

Starting from correspongding olefins, eight chiral β-aminoalcohols were synthesized by Sharpless asymmetric dihydroxylation and applied in the organocatalytic asymmetric epoxidation of α,β-enones. The effects of the amount of catalysts, the structure of catalysts, oxidant, solvent and reaction temperature on enantioselectivity were also studied. When the amount of catalyst was 30 mol% relative to α,β-enones, tert-butyl hydroperoxide (TBHP) as oxidant, hexane as a solvent at room temperature, (1S,2R)-1,2-diphenyl- 2-(N-methyl)aminoethanol (3) has been successfully applied as catalyst in asymmetric epoxidation of α,β-enones with the yield up to 84% and enantiomeric excesses up to 70%.

Key words: α,β-enone, chiral β-aminoalcohol, asymmetric catalysis, asymmetric epoxidation