某些官能化手性氮杂环丙烷衍生物的合成及其结构  

Synthesis and Structure of Some Functionalized Chiral Aziridine Derivatives

作　　者：王建平[1] 程习星[2] 陈庆华[1] 

机构地区：[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

出　　处：《化学学报》2006年第7期686-690,共5页Acta Chimica Sinica

基　　金：国家自然科学基金(No.29672004)资助项目.

摘　　要：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,1HNMR,13CNMR,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.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.

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 

分 类 号：O626[理学—有机化学] TQ654.2[理学—化学]