Recent Advances in Transition‐Metal‐Catalyzed Thiolation and Sulfonylation of Alkenes

The development of efficient and selective strategies for constructing CS bonds has garnered significant attention in organic and medicinal chemistry, owing to the widespread presence of this linkage in biologically active molecules, pharmaceuticals, agrochemicals, and functional materials. Among the various approaches, alkene thiolation and sulfonylation stand out as one of the most straightforward methods for organosulfur synthesis, enabling the direct introduction of sulfur‐containing functionalities into unsaturated hydrocarbons. This review provides a comprehensive summary of recent advances (2013–present) in transition‐metal‐catalyzed CS bond formation via alkene thiolation and sulfonylation. We systematically discuss the synthetic methodologies, including transition‐metal‐catalyzed hydrothiolation, carbothiolation, hydrosulfonylation, and carbosulfonylation, highlighting their respective substrate scope, chemoselectivity, regioselectivity, enantioselectivity, and reaction mechanisms. By consolidating the latest developments and critical perspectives, this review aims to serve as a valuable resource for researchers, encouraging further exploration and innovation in this dynamic field. The continued evolution of transition‐metal‐catalyzed CS bond formation is expected to unlock new opportunities in drug discovery, materials science, and synthetic methodology.