Rhodium catalysts for C–S bond formation

Sulfur-containing molecules are commonly found in chemical biology, organic synthesis, and materials chemistry. The preparation of these compounds through traditional methods usually required harsh reaction conditions. The use of transition-metal-based catalysts has allowed the development of more efficient and sustainable synthetic processes. Rhodium-catalyzed C–S bond formation through the reaction between sulfur sources such as S8, thiols, or disulfides with organic substrates such as alkynes, allenes, and aryl/alkyl halides is one of the most important methods in the synthesis of thioethers. Here, we summarize recent efforts in the reactions of cross coupling, C–H activation, metathesis, thiolation, carbothiolation, and hydrothiolation for the C–S bond formation catalyzed by rhodium complexes, particularly highlighting the synthetic and mechanistic aspects.