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

doi:10.6023/cjoc202508022

Chinese Journal of Organic Chemistry

ARTICLE

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

^a绍兴文理学院化学化工学院绍兴 312000;
^b浙江省脂溶性维生素工程中心绍兴 312000

收稿日期:2025-08-25 修回日期:2025-10-15
基金资助:
绍兴市基础公益项目(No. 2023A11003 )和绍兴文理学院科研基金(No. 2023LG003)资助项目.

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

Chao Ma^a, Xiaoling Xu^a, Xiang Luo^a, Ruijuan Lu^a, Guoqi Yu^*,b, Tao Cai^*,a,b

^aCollege of Chemistry and Chemical Engineering, Shaoxing University, Shaoxing, 312000;
^bZhejiang Engineering Research Center of Fat-Soluble Vitamin, Shaoxing University, Shaoxing, 312000

Received:2025-08-25 Revised:2025-10-15
Contact: *E-mail: yuguoqi@usx.edu.cn; cait361@usx.edu.cn
Supported by:
Shaoxing Basic Public Welfare Project (No. 2023A11003), and the Research Project of Shaoxing University (No. 2023LG003)

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Abstract

This study presents the first electrochemical method that employs commercially available, stable, and inexpensive thiophenols as sulfenylating agents for the efficient synthesis of valuable 4-sulfenylisocoumarins. 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, significantly broadens the substrate scope, and offers a practical and sustainable alternative for the synthesis of 4-sulfenylisocoumarins.

Key words: 4-Sulfenylisocoumarins, thiophenol, o-alkynylbenzoates, electrochemical synthesis, radical cascade annulation

Cite this article

Chao Ma, Xiaoling Xu, Xiang Luo, Ruijuan Lu, Guoqi Yu, Tao Cai. Electrochemical Synthesis of 4-Sulfenylisocoumarins via Radical Cascade Annulation of o-Alkynylbenzoates with Thiophenols[J]. Chinese Journal of Organic Chemistry, doi: 10.6023/cjoc202508022.

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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

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

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