Chinese Journal of Organic Chemistry ›› 2020, Vol. 40 ›› Issue (10): 3410-3419.DOI: 10.6023/cjoc202005066 Previous Articles     Next Articles


朱海倩a, 商甜波a, 卢增辉b, 罗芳a, 朱钢国a   

  1. a 浙江师范大学化学系 先进催化材料教育部重点实验室 浙江金华 321004;
    b 万州区生态环境监测站 重庆 404000
  • 收稿日期:2020-05-24 修回日期:2020-06-06 发布日期:2020-06-13
  • 通讯作者: 朱钢国
  • 基金资助:

Visible-Light Photocatalytic Remote Halo-difluoroalkylation of Thioalkynes

Zhu Haiqiana, Shang Tianboa, Lu Zenghuib, Luo Fanga, Zhu Gangguoa   

  1. a Key Laboratory of the Ministry of Education for Advanced Catalysis Materials, Department of Chemistry, Zhejiang Normal University, Jinhua, Zhejiang 321004;
    b Wanzhou Ecological Environment Monitoring Station, Chongqing 404000
  • Received:2020-05-24 Revised:2020-06-06 Published:2020-06-13
  • Supported by:
    Project supported by the National Natural Science Foundation of China (No. 21672191), the Natural Science Foundation of Zhejiang Province (No. LZ20B020002) and the Education Department of Zhejiang Province (No. Y201942955).

Fluoroalkylated alkenes are of significant importance in life sciences and functional materials. The fluoroalkylation of alkynes offers an efficient method for the synthesis of functionalized fluoroalkylated alkenes. However, the current methods are often limited to 1,2-difunctionalization, while the remote fluoroalkylative difunctionalization of alkynes has been rarely developed. Herein, a novel visible-light-induced remote halo-difluoroalkylation of thioalkynes is realized with difluoroalkyl halides as the radical source, forming distally halogenated (Z)-fluoroalkylated alkenes in moderate to high yields with excellent regio-, stereo-, and site-selectivity. The notable features of this reaction include the mild reaction conditions, broad substrate scope, concurrent formation of three new chemical bonds, and a thermodynamically less stable (Z)-alkene, thus enabling it a highly attractive method for organic synthesis. It represents a new advance on the direct C-H bond halogenation. Preliminary mechanistic studies indicate a cascade radical process involving the heteroatom-induced β-fluoroalkylation of C-C triple bonds, intramolecular 1,5-hydrogen atom transfer (1,5-HAT), single electron transfer (SET) oxidation and halide addition.

Key words: difluoroalkyl, visible-light photoredox catalysis, thioalkyne, C-H halogenation, radical, selectivity