Catalytic Reactions of Alkynyl Sulfides: Versatile Tools in Synthetic Chemistry

Abstract Alkynyl sulfides, a significant class of heteroatom‐substituted alkynes, have garnered considerable attention within the synthetic community because of their distinctive characteristics, such as the enhanced reactivity, precise selectivity control, and facile derivatization via C−S bond couplings. Their transformations can provide a direct access to functionalized organosulfur and even sulfur‐free compounds in a highly regio‐ and stereoselective manner, which is very attractive for many fields, including organic synthesis, material science, medicinal chemistry, and life science. This review summarizes the recent progresses on catalytic reactions of alkynyl sulfides, such as the transition‐metal‐catalyzed controllable functionalizations, including hydro‐, hetero‐, and carbofunctionalizations, electrophilic additions, radical addition‐initiated functionalizations, and formal [2+n] cycloadditions, in which the reaction mechanism, selectivity control, scope and limitations are discussed in detail. Given the rapidly increasing interests and applications of sulfur‐containing compounds in both chemistry and life science, it can be anticipated that this review will be valuable for synthetic chemists and may contribute further development of the alkynyl sulfide chemistry.