Chin. J. Org. Chem. ›› 2018, Vol. 38 ›› Issue (5): 1172-1176.DOI: 10.6023/cjoc201711050 Previous Articles     Next Articles

Articles

以炔为原料可调控合成碘代炔和二碘代烯烃

陈锁a, 章晓炜a, 赵辉b, 郭晓红a, 胡祥国a   

  1. a 江西师范大学国家单糖化学合成工程技术研究中心 南昌 330022;
    b 安徽省应用技术研究院有效成分提取分离研究中心 合肥 230031
  • 收稿日期:2017-11-30 修回日期:2018-01-08 出版日期:2018-05-25 发布日期:2018-01-26
  • 通讯作者: 章晓炜,E-mail:xwzhang@jxnu.edu.cn;胡祥国,E-mail:huxiangg@iccas.ac.cn E-mail:xwzhang@jxnu.edu.cn;huxiangg@iccas.ac.cn
  • 基金资助:

    国家自然科学基金(No.21502076)、合肥市百人计划、江西省杰出青年人才计划(No.20171BCB23039)资助项目.

Switchable Synthesis of Iodoalkynes and Diiodoalkenes from Terminal Alkynes

Chen Suoa, Zhang Xiaoweia, Zhao Huib, Guo Xiaohonga, Hu Xiangguoa   

  1. a National Engineering Research Center for Carbohydrate Synthesis, Jiangxi Normal University, Nanchang 330022;
    b Anhui Engineering Technology Research Center for Extraction and Isolation of Active Components, Anhui Academy of Applied Technology, Hefei 230031
  • Received:2017-11-30 Revised:2018-01-08 Online:2018-05-25 Published:2018-01-26
  • Contact: 10.6023/cjoc11050 E-mail:xwzhang@jxnu.edu.cn;huxiangg@iccas.ac.cn
  • Supported by:

    Project supported by the National Natural Science Foundation of China (No. 21502076), the Hundred-Talent Program of Hefei City and the Outstanding Young Talents Scheme of Jiangxi Province (No. 20171BCB23039).

Iodoalkynes and diiodoalkenes are valuable intermediates used extensively for C—C, C—O and C—N bonds formation. Therefore, the development of new method for the synthesis of these compunds is desirable. In this work, a novel and switchable protocol for the synthesis of iodoalkynes and diiodoalkenes has been developed, which were formed from terminal alkynes using the same reagent system of ZnI2 and tert-butyl nitrite in the presence or absence of triethylamine, respectively. The iodoalkyne formation is operationally simple, mild (weak base and room temperature), and tolerant of a large range of functional groups. In contrast, the diiodoalkene transformation shows interesting dependence on the electron property, and only electron-rich and neutral compounds are viable substrates. The control experiments performed suggest that iodoalkynes and diiodoalkenes are not interchangeable under a series of reaction conditions, including the optimized conditions, which can be explained by the mechanism in which both of the reactions involve a iodonium intermediate formed directly from a terminal alkyne.

Key words: iodoalkyne, diiodoalkene, tert-butyl nitrite, alkyne, zinc iodide