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化学学报
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化学学报 ›› 2006, Vol. 64 ›› Issue (7): 686-690. 上一篇    下一篇

研究论文

某些官能化手性氮杂环丙烷衍生物的合成及其结构

王建平1，程习星2，陈庆华*,1   

  1. (1洛阳师范学院化学系 洛阳 471022)
    (2河南科技大学化工与制药学院 洛阳 471003)
  • 投稿日期:2005-09-08 修回日期:2005-12-16 发布日期:2006-04-15
  • 通讯作者: 陈庆华

Synthesis and Structure of Some Functionalized Chiral Aziridine Derivatives

WANG Jian-Ping1, CHENG Xi-Xing2, CHEN Qing-Hua*,1   

  1. (1 Department of Chemistry, Luoyang Normal College, Luoyang 471022)
    (2 College of Chemical Engineering and Pharmaceutics, Henan University of Science and Technology, Luoyang 471003)
  • Received:2005-09-08 Revised:2005-12-16 Published:2006-04-15
  • Contact: CHEN Qing-Hua

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866

被引次数

53

手性元5-(R)-(1R,2S,5R)-孟氧基-3-溴-2(5H)-呋喃酮(3)与氮亲核试剂伯胺(4), 通过串联的不对称Michael加成/分子内亲核取代反应得到了具有两个新的手性中心的1R,5S-6-烷基-6-氮杂-2R-孟氧基-3-氧杂-4-氧代二环[3,1,0]己烷(5a～5d), 产率41%～51%, e.e.≥98%. 后者经LiAlH4还原得到N-烷基-2,3-双(羟甲基)氮杂环丙烷(6a～6d), 产率66%～91%. 化合物5和6通过元素分析, IR, 1H NMR, 13C NMR, MS以及X射线晶体分析, 测定了它们的化学结构及立体化学构型. 本文为N-烷基氮杂环丙烷类化合物的合成提供了一种有效途径.

关键词: 串联的不对称合成, 氮杂环丙烷衍生物, 光学活性, 晶体结构

The chiral 1R,5S-6-alkyl-6-aza-2R-menthoxy-3-oxa-4-oxobicyclo[3,1,0]hexane (5a～5d) containing two stereogenic centers were obtained in 41%～51% yields with e.e.≥98% via the tandem asymmetric Michael addition and internal nucleophilic substitution reaction of the chiron 3 with the primary amine 4 as a nucleophile. After the effective reduction of compounds 5 by LiAlH4 in THF, the target molecules, meso-N-alkyl-2,3-bis(hydroxymethyl)aziridines (6a～6d) were obtained in 66%～91% yields. The chemical structures of 5 and 6 were readily confirmed by analytical and spectroscopic data. The proposed structures of optically active compounds were consistent with the stereochemistry and configuration of their molecules further confirmed by the X-ray crystallography of 5a and 6c. These results could provide a new synthetic route to the functionalized optically active aziridine derivatives.

Key words: tandem asymmetric reaction, aziridine derivative, optical activity, crystal structure