近日，湖北师范大学殷国栋团队实现了通过S-to-C原子交换对苯二硫-3-酮进行骨架编辑。相关论文于2025年11月4日发表在《中国化学》杂志上。

研究组开发了一种有机膦介导的苯并二硫醇-3-酮骨架编辑新方法，实现了无金属条件下通过硫-碳原子交换改造苯并二硫醇-3-酮结构的首例报道。该突破性策略基于苯并二硫醇-3-酮与α-卤代羰基化合物的形式[4+1]环加成反应，可依据α-卤代羰基底物的取代模式，分别高效合成3-羟基苯并[b]噻吩与苯并[b]噻吩-3(2H)-酮两类杂环产物。

新开发的硫-碳交换技术通过"硫原子剔除-碳原子插入"实现了重要硫杂环的高效构建。该方法具有无过渡金属参与、无需惰气保护、操作简便、条件温和、底物普适性广及收率良好等突出优势。值得注意的是，该策略可成功应用于结构多样生物活性分子的后期官能化，充分展现了这种无金属骨架编辑策略的应用潜力与实用价值。

附：英文原文

Title: Skeletal Editing of Benzodithiol-3-ones via S-to-C Atom Swap

Author: Xiaobing Liu, Xuan Kong, Jing Zheng, Jiayuan Zhou, Jinghui Wen, Yao Zhou, Shengzhou Jin, Guodong Yin

Issue&Volume: 2025-11-04

Abstract: 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.

DOI: 10.1002/cjoc.70350

Source: https://onlinelibrary.wiley.com/doi/10.1002/cjoc.70350