Carbon–sulfur bond formation represents a key step in the synthesis of thioethers, which are a common structural motif in many pharmaceutically compounds. The direct cross-dehydrogenative coupling of C–H/S–H bonds has become a powerful tool for C–S bond formation. As these coupling reactions avoid pre-functionalization of the starting materials, they are more atom-economical, practical, and environmentally friendly than traditional cross-coupling reactions. In this review, we will highlight the most important developments in this novel and interesting research arena with the emphasis on the mechanistic aspects of the reactions. The review is divided into three major sections: (1) C(sp³)-H/S–H bonds coupling reactions; (2) C(sp²)-H/S–H bonds coupling reactions; and (3) C(sp)-H/S–H bonds coupling reactions.

碳-硫键的形成代表合成硫醚的关键步骤，硫醚是许多药物化合物中常见的结构基序。C–H / S–H键的直接交叉脱氢偶联已成为形成C–S键的强大工具。由于这些偶联反应避免了原料的预功能化，因此与传统的交叉偶联反应相比，它们在原子经济，实用和环境友好方面都更为出色。在这篇综述中，我们将重点介绍这一新颖有趣的研究领域中最重要的进展，重点是反应的机理方面。该综述分为三个主要部分：（1）C（sp ³）-H / S-H键偶联反应；（2）C（sp ²）-H / S–H键耦合反应；（3）C（sp）-H / S–H键偶联反应。