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有机化学 ›› 2009, Vol. 29 ›› Issue (10): 1611-1616. 上一篇    下一篇

研究论文

氮叶立德高立体选择性地合成螺[环丙烷-1,4'-吡唑啉-5'-酮] 衍生物的研究

王 猛a   张 慧*,a   陈 杰a   吴小余a   邓红梅b   邵 敏b   曹卫国*,a,c   

  1. (a上海大学化学系 上海 200444) (b上海大学分析测试中心 上海 200444) (c中国科学院上海有机化学研究所金属有机化学国家重点实验室 上海 200032)
  • 收稿日期:2009-01-15 修回日期:2009-04-10 发布日期:2009-05-19

Highly Stereoselective Synthesis of Spiro[cyclopropane-1,4'- pyrazolin-5'-one] Derivertives via Ammonium Ylide

Wang, Menga   Zhang, Hui*,a   Chen, Jiea   Wu, Xiaoyua   Deng, Hongmeib   Shao, Minb   Cao, Weiguo*,a,c   

  1. (a Department of Chemistry, Shanghai University, Shanghai 200444) (b Instrumental Analysis and Research Center, Shanghai University, Shanghai 200444) (c State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032)
  • Received:2009-01-15 Revised:2009-04-10 Published:2009-05-19

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螺环丙基杂环化合物是一类具有重要药理、生理活性的化合物, 研究和发展这类化合物的新的立体选择性合成方法是当前有机合成领域的一个热点. 对1,4-二氮杂双环[2.2.2]辛环(DABCO)衍生的氮叶立德与3-甲基-1-苯基-4-芳亚甲基-5-吡唑啉酮合成螺环丙基吡唑啉酮的反应做了研究, 并与胂叶立德所参与的类似反应的结果做了比较, 发现仅得到单一反式结构产物, 但存在exo和endo两种构型, 其中前者为主要产物. 产物结构由IR, MS, 1H NMR, 13C NMR, 元素分析和X射线衍射鉴定. 还从反应机理角度对两种叶立德性质对反应的影响做了解释.

关键词: 螺环丙基, 氮叶立德, 立体选择性合成

Spirocyclopropane-annulated heterocycles are a fundamental class of bioactive natural and nonnatural molecules. Their importance is reflected in the enormous effort that has been invested in their diastereo- and enantioselective synthesis. In this paper, the stereoselective construction of the derivatives of spiro[cyclopropane-1,4'-pyrazolin-5'-one] via ammonium ylides was reported. The results were compared with those of the similar reaction via arsonium ylide. In the reaction, only the trans spirocyclopropanes were obtained. The exo and endo isomers were also provided with the former being the major. The structures of products were identified by IR, MS, 1H NMR, elemental analysis and X-ray diffraction analysis. The mechanism was proposed to explain the different influence of ammonium or arsonium ylide on the reaction.

Key words: spirocyclopropyl, ammonium ylide, stereoselective synthesis