有机化学 ›› 2026, Vol. 46 ›› Issue (3): 1039-1049.DOI: 10.6023/cjoc202508022 上一篇    下一篇

研究论文

电化学促进邻炔基苯甲酸酯与硫酚的自由基串联环化反应合成4-硫代异香豆素

马超a, 徐晓玲a, 骆翔a, 鲁瑞娟a, 虞国棋b,*(), 蔡涛a,b,*()   

  1. a 绍兴文理学院化学化工学院 浙江绍兴 312000
    b 浙江省脂溶性维生素工程中心 浙江绍兴 312000
  • 收稿日期:2025-08-25 修回日期:2025-10-15 发布日期:2025-11-27
  • 通讯作者: 虞国棋, 蔡涛
  • 基金资助:
    绍兴市基础公益项目(2023A11003); 绍兴文理学院科研基金(2023LG003)

Electrochemical Synthesis of 4-Sulfenylisocoumarins via Radical Cascade Annulation of o-Alkynylbenzoates with Thiophenols

Chao Maa, Xiaoling Xua, Xiang Luoa, Ruijuan Lua, Guoqi Yub,*(), Tao Caia,b,*()   

  1. a College of Chemistry and Chemical Engineering, Shaoxing University, Shaoxing, Zhejiang 312000
    b Zhejiang Engineering Research Center of Fat-Soluble Vitamin, Shaoxing University, Shaoxing, Zhejiang 312000
  • Received:2025-08-25 Revised:2025-10-15 Published:2025-11-27
  • Contact: Guoqi Yu, Tao Cai
  • Supported by:
    Shaoxing Basic Public Welfare Project(2023A11003); Research Project of Shaoxing University(2023LG003)

报道了一种在电化学条件下, 直接使用市售、稳定且廉价的硫酚作为硫化试剂构建4-硫代异香豆素类化合物的方法. 在优化后的反应条件下, 各种带吸电子基和给电子基的芳基硫酚均能与邻炔基苯甲酸酯顺利反应, 以中等到良好的收率得到相应的4-硫代异香豆素衍生物, 展现出优异的底物普适性. 初步机理研究表明, 该电化学促进的串联环化反应可能涉及自由基路径. 与文献方法相比, 该策略避免了使用对水敏感的预官能团化试剂, 如芳基硫氯(ArSCl)、二芳基二硫化物(ArSSAr)和N-硫代琥珀酰亚胺, 显著拓宽了底物适用范围.

关键词: 4-硫代异香豆素, 苯硫酚, 邻炔基苯甲酸酯, 电化学合成, 串联环化

The first electrochemical method that employs commercially available, stable, and inexpensive thiophenols as sulfenylating agents for the efficient synthesis of valuable 4-sulfenylisocoumarins is presented. Various thiophenols containing both electron-donating and electron-withdrawing groups reacted smoothly with o-alkynylbenzoates to afford the corresponding 4-sulfenylisocoumarins in moderate to good yields. Preliminary mechanistic investigation, including controlled experiments and cyclic voltammetry (CV) experiments, indicated that this electrochemical cyclization might proceed via a radical pathway. In comparison to existing methods, this strategy circumvents the need for moisture-sensitive and pre-functionalized sulfenylating reagents, such as aryl sulfenyl chloride (ArSCl), diaryl disulfide (ArSSAr) and N-thiosuccinimide, significantly broadens the substrate scope, and offers a practical and sustainable alternative for the synthesis of 4-sulfenylisocoumarins.

Key words: 4-sulfenylisocoumarin, thiophenol, o-alkynylbenzoate, electrochemical synthesis, radical cascade annulation