Alkynyl Sulfonium Salts Can Be Employed as Chalcogen-Bonding Catalysts and Generate Alkynyl Radicals under Blue-Light Irradiation.

Chalcogen bonding (ChB) has emerged as a promising tool in organic synthesis. However, compared with the well-developed selenium- and tellurium-based salt catalysts, the ChB catalysis of sulfonium salts is still unknown. Here, we report a new type of alkynyl-sulfonium salt ChB catalysis for various ionic transformations, including transfer hydrogenation, bromination, bromolactonization, dimerization of 1,1-diphenylethylene, nitro-Michael addition reaction and Ritter reaction. More importantly, the photocapability of ChB was first demonstrated to generate alkynyl radicals for the synthesis of a variety of chalcogenoacetylenes. Mechanistic studies shed light on the mechanism of the photoinduced reactions and confirmed the involvement of alkynyl radicals which are difficult to generate otherwise.