有机化学 ›› 2014, Vol. 34 ›› Issue (7): 1369-1375.DOI: 10.6023/cjoc201402005 上一篇    下一篇

研究论文

铁催化2-烯基氮杂芳烃的绿色合成

刘森生a, 姜坤a, 皮单违a, 周海峰a,b, Yasuhiro Uozumib, 邹坤a   

  1. a 三峡大学生物与制药学院 天然产物研究与利用湖北省重点实验室 宜昌 443002;
    b 分子科学研究所 冈崎市 日本 444-8787
  • 收稿日期:2014-02-05 修回日期:2014-03-22 发布日期:2014-04-02
  • 通讯作者: 周海峰 E-mail:haifeng-zhou@hotmail.com
  • 基金资助:

    国家自然科学青年基金(No.21202092)和三峡大学人才科研启动基金(No.KJ2012B080)资助项目

Iron-Catalyzed Green Synthesis of 2-Alkenylazaarenes

Liu Senshenga, Jiang Kuna, Pi Danweia, Zhou Haifenga,b, Uozumi Yasuhirob, Zou Kuna   

  1. a Hubei Key Laboratory of Natural Products Research & Development, College of Biological & Pharmaceutical Sciences, China Three Gorges University, Yichang 443002;
    b Institute for Molecular Science, Okazaki, Japan 444-8787
  • Received:2014-02-05 Revised:2014-03-22 Published:2014-04-02
  • Supported by:

    Project supported by the National Natural Science Foundation of China (No. 21202092) and the Startup Foundation from China Three Gorges University (No. KJ2012B080).

以廉价、低毒的醋酸亚铁为催化剂,在三氟乙酸助催化下,2-甲基氮杂芳烃与芳香醛经过加成与脱水反应,直接选择性合成具有生物活性的反式2-烯基氮杂芳烃化合物,水是唯一副产物. 该合成方法催化剂用量少,后处理方便,产率高,选择性高,底物适用范围广. 治疗哮喘药顺尔丁中间体(E)-3-[2-(7-氯-2-喹啉基)乙烯基]苯甲醛(3v)的克级合成展现了该方法的应用前景.

关键词: 烯基化, 含氮杂环, C-H活化, 绿色化学

A straightforward and selective synthesis of bioactive trans-2-alkenylazaarenes has been achieved via cheap and nontoxic iron(II) acetate catalyzed addition and dehydration reactions of 2-methylazaarenes and aromatic aldehydes in the presence of catalytic amount of trifluoroacetic acid with water as the only byproduct. The low catalyst loading, convenience, good yield, high selectivity, as well as the broad substrate scope make this protocol very practical. The practical potential was also demonstrated by gram-scale synthesis of (E)-3-[2-(7-chloro-2-quinolinyl)ethenyl]benzaldehyde (3v), an intermediate of Singulair.

Key words: alkenylation, nitrogen heterocycles, C-H activation, green chemistry