Synthesis of Aryl Sulfides by Metal‐Free Arylation of Thiols with Diaryliodonium Salts under Basic Conditions

Metal‐free arylation of thiols with diaryliodonium salts has been developed. The application of a strong organic base enables the C−S bond formation under mild and experimentally simple conditions. The method allows for the synthesis of aryl sulfides containing a broad range of aryl groups from an array of thiols, including aryl, heteroaryl, and alkyl ones. The mechanism of the reaction was studied by DFT calculations, demonstrating that it proceeds via the inner sphere pathway involving formation of an Ar2I(SR) intermediate, followed by reductive elimination. Aryl sulfides are synthesized by metal‐free arylation of thiols with diaryliodonium salts under basic conditions. The protocol features easy performance, mild conditions, and short reaction time. It provides access to an array of products, including such that contain complex moieties of biological and therapeutic relevance (e. g., heterocycles, a carbohydrate). DFT calculations demonstrate that the reaction proceeds via the formation of Ar2I(SR) intermediate, followed by the C−S forming reductive elimination.