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化学学报
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化学学报 ›› 2007, Vol. 65 ›› Issue (16): 1643-1648. 上一篇    下一篇

研究论文

3-(噻吩-2-基)-β-内酰胺的合成及其立体化学

李伯男, 梁勇, 焦雷, 胡立博, 杜大明, 许家喜*   

  1. (北京分子科学国家实验室(BNLMS) 生物有机与分子工程教育部重点实验室 北京大学化学与分子工程学院 北京 100871)
  • 投稿日期:2007-03-29 修回日期:2007-05-06 发布日期:2007-08-28
  • 通讯作者: 许家喜

Synthesis and Stereochemistry of 3-(Thiophen-2-yl)-β-lactams

LI Bo-Nan; LIANG Yong; JIAO Lei; HU Li-Bo; DU Da-Ming; XU Jia-Xi*   

  1. (Beijing National Laboratory for Molecular Sciences (BNLMS), Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871)
  • Received:2007-03-29 Revised:2007-05-06 Published:2007-08-28
  • Contact: XU Jia-Xi

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Staudinger 反应是合成β-内酰胺类化合物最重要的方法之一. 3-(噻吩-2-基)-β-内酰胺是一类重要的β-内酰胺类衍生物. 发展了一种从1-(噻吩-2-基)-4,4,4-三氟-1,3-丁二酮和对甲苯磺酰叠氮方便地制备1-(噻吩-2-基)-2-重氮基乙酮的新方法, 利用1-(噻吩-2-基)-2-重氮基乙酮加热分解生成的噻吩-2-基烯酮参与的Staudinger反应合成了一系列3-(噻 吩-2-基)-β-内酰胺衍生物, 并研究了噻吩-2-基烯酮参与的Staudinger反应的立体选择性. 实验结果表明噻吩-2-基烯酮是比苯基烯酮更富电子的Moore烯酮, 其电子性质介于对甲氧基苯基烯酮和对甲基苯基烯酮之间.

关键词: β-内酰胺, Staudinger反应, 立体选择性, 重氮酮, 烯酮

The Staudinger reaction is one of the most important methods in synthesis of β-lactams. 3-(Thiophen-2-yl)-β-lactam is one class of important β-lactam derivatives. A convenient and new method was developed to synthesize 2-diazo-1-(thiophen-2-yl)-ethanone from 4,4,4-trifluoro-1-(thiophen-2-yl)- 1,3-butanedione and tosyl azide. A series of 3-(thiophen-2-yl)-β-lactams were synthesized via the Staudinger reaction of imines and thiophen-2-ylketene generated thermally from 2-diazo-1-(thiophen-2-yl)-ethanone. The stereoselectivity of the Staudinger reaction was also investigated. The results indicate that thiophen-2-ylketene is a more electron-rich Moore ketene than phenylketene and its electronic property locates between those of 4-methoxyphenylketene and 4-methylphenylketene.

Key words: β-lactam, Staudinger reaction, stereoselectivity, diazoketone, ketene