The Palladium Catalyzed Nucleophilic Substitution of Aryl Halides by Thiolate Anions

Abstract In the presence of a catalytic amount of tetrakis(triphenylphosphine) palladium, phenyl and methyl or methoxyphenyl iodides and bromides were found to react with thiolate anions in alcoholic solvents, to give the corresponding aryl sulfides in excellent yield. The reaction is useful to prepare symmetrical or unsymmetrical diaryl sulfides and aryl alkyl sulfides. The reaction mechanism does not involve aryl halide radical anions, but is thought to involve oxidative addition of aryl halide to Pd(0), nucleophilic substitution on the adduct followed by reductive elimination.