The construction of C(sp³)–S bonds through C(sp³)–H activation holds significant value in the synthesis of sulfides. However, the vast majority of strategies primarily involve the use of electron-rich sulfur sources (such as sulfinates and thioalcohols) to thiolate activated and thermodynamically favored C(sp³)–H bonds. Therefore, further expanding the substrate range of sulfur sources and various C(sp³)–H bonds would provide an entry for the synthesis of unique structural molecules. Here, we report a FeCl₃/HCl synergistic catalytic approach that enables the formation of C(sp³)–S bonds via reductive deoxygenation cross-coupling of activated/inert C(sp³)–H and aryl/alkyl sulfonyl chlorides without the need for external reductants. Mechanism studies reveal that HCl plays a crucial role in the thiolation of inert C(sp³)–H bonds, not only enhancing the catalytic activity of FeCl₃ but also forming electron donor–acceptor (EDA) complexes with sulfonyl chlorides.

中文翻译：

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通过光诱导配体-金属电荷转移将 C（sp3）–H 与磺酰氯铁催化的硫醇化


通过 C（sp³）-H 活化构建 C（sp³）-S 键在硫化物的合成中具有重要价值。然而，绝大多数策略主要涉及使用富电子硫源（如亚磺酸盐和硫醇）来硫代化活化和热力学上有利的 C（sp³）-H 键。因此，进一步扩大硫源和各种 C（sp³）-H 键的底物范围将为合成独特结构分子提供入口。在这里，我们报道了一种 FeCl₃/HCl 协同催化方法，该方法能够通过活化/惰性 C（sp³）-H 和芳基/烷基磺酰氯的还原脱氧交叉偶联形成 C（sp³）-S 键，而无需外部还原剂。机理研究表明，HCl 在惰性 C（sp³）-H 键的硫醇化中起着至关重要的作用，不仅增强了 FeCl₃ 的催化活性，而且还与磺酰氯形成电子供体-受体 （EDA） 复合物。