某些官能化手性氮杂环丙烷衍生物的合成及其结构

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.

Synthesis and Structure of Some Functionalized Chiral Aziridine Derivatives

The chiral 1R,5S-6-alkyl-6-aza-2R-menthoxy-3-oxa-4-oxobicyclo3,1,0]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.