有机化学 ›› 2017, Vol. 37 ›› Issue (12): 3242-3247.DOI: 10.6023/cjoc201711015 上一篇    下一篇

研究论文

碘催化的咪唑类化合物N-H键的官能化

杨丽烽, 惠人杰, 单恒悦, 巩凯   

  1. 江南大学药学院 无锡 214122
  • 收稿日期:2017-11-08 修回日期:2017-12-04 发布日期:2017-12-08
  • 通讯作者: 巩凯 E-mail:gongkai@jiangnan.edu.cn
  • 基金资助:

    国家自然科学基金(No.51303069)、江苏高校品牌专业建设工程(No.PPZY2015B146)资助项目.

Iodine-Catalyzed Functionalization of N-H Bond of Imidazoles

Yang Lifeng, Hui Renjie, Shan Hengyue, Gong Kai   

  1. School of Pharmaceutical Science, Jiangnan University, Wuxi 214122
  • Received:2017-11-08 Revised:2017-12-04 Published:2017-12-08
  • Contact: 10.6023/cjoc201711015 E-mail:gongkai@jiangnan.edu.cn
  • Supported by:

    Project supported by the National Natural Science Foundation of China (No. 51303069), and the Top-Notch Academic Programs Project of Jiangsu Higher Education Institutions (No. PPZY2015B146).

由于苯并咪唑结构的化合物在抗肿瘤、抗高血压等方面具有卓越的生物活性,以I2作为催化剂,叔丁基过氧化物(DTBP)作为氧化剂,成功实现了一系列咪唑类化合物与环状醚、环状硫醚α-C(sp3)-H键的交叉脱氢偶联反应,完成了咪唑类化合物N-H键的官能团化,合成了一系列具有生物活性的化合物.经过反应机理的研究,推测该类反应可能是以亚胺/硫亚胺离子作为活性中间体进行反应以实现在N-H健的官能团修饰.

关键词: 碘, N-H键官能化, 环醚, 交叉脱氢偶联, 环硫醚

Since benzimidazole containing moieties have a lot of pharmacological activities, we reported the ageneral metal-free and cost-effective, I2/DTBP-catalyzed method for the functionalization of N-H bonds of azoles via α-C(sp3)-H activation of cyclic ethers or cyclic thioethers. And this method is also applicable to a diverse range of N-substituted azoles and cyclic ethers/thioethers. By using the free-radical scavenger 2,2,6,6-tetramethylpiperidin-1-oxyl (TEMPO) as a control, we suggest that a radical/SET mechanism proceeding via a radical/oxonium or thionium ion may be involved in the reaction.

Key words: iodine, functionalization of N-H bond, cyclic ether, cross dehydrogenative coupling, cyclic thioether