Palladium-Catalyzed Amination of Aryl Sulfides with Anilines

A combination of a palladium-NHC catalyst and potassium hexamethyldisilazide enables the amination of aryl sulfides with anilines to afford a wide variety of diarylamines. The reaction conditions are versatile enough for the reaction of even bulky ortho-substituted aryl sulfides. This amination can be applied to the modular synthesis of N-aryl carbazoles from the corresponding ortho-bromothioanisoles. As aryl sulfoxides undergo extended Pummerer reactions to afford ortho-substituted aryl sulfides, the Pummerer products are thus useful substrates for the amination to culminate in efficient syntheses of a 2-anilinobenzothiophene and an indole as proof-ofprinciple of the utility of the extended Pummerer reaction/amination cascade.