Skeletal Editing of Benzodithiol-3-ones via S-to-C Atom Swap
Xiaobing Liu , Xuan Kong , Jing Zheng , Jiayuan Zhou , Jinghui Wen , Yao Zhou , Shengzhou Jin , Guodong Yin
Chinese Journal of Chemistry ›› 2026, Vol. 44 ›› Issue (2) : 251 -258.
An expedient organophosphine-mediated skeletal editing of benzodithiol-3-ones is demonstrated herein, which represents the first example for metal-free transformations of benzodithiol-3-ones via S-to-C atom swap. This unprecedented formal [4+1] cycloadditions of benzodithiol-3-ones and α-halocarbonyls enable divergent synthesis of diverse 3-hydroxybenzo[b]thiophenes and benzo[b]thiophen-3(2H)-ones, the products of which were determined by the substitution pattern of the α-halocarbonyls. The newly-developed S-to-C exchange strategy allows for the streamline assembly of valuable sulfur-heterocycles via sulfur-deletion and carbon-insertion. This method is distinguished by its transition-metal-free nature, elimination of inert gas protection requirements, convenient operation, mild conditions, extensive substrate generality and decent yields. Of note, the current protocol could be readily applied to late-stage diversification of structurally varied bioactive molecules, underscoring the potential applicability and practical utility of this metal-free skeletal editing strategy.
Skeletal editing / Benzodithiol-3-ones / Benzo[b]thiophenes / Cleavage reactions / Metal-free / Cyclization / Sulfur-heterocycles / Atom swap
2025 SIOC, CAS, Shanghai, & WILEY-VCH GmbH
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