Iodine/DMSO-Promoted Selective Direct Arylthiation of Anilines with Thiols under Metal-Free Conditions.

An iodine-promoted divergent thiolation of unprotected anilines with thiols for the synthesis of sulfide anilines has been described. The combinational use of I and DMSO played an important role to realize this kind of transformation without the aid of a metal catalyst and strong oxidants. The reaction selectivity was well controlled to provide mono-, bis-, and trisubstituted diaryl sulfide derivatives. More importantly, iodination and sulfenylation can occur simultaneously to provide useful multifunctionalized iodoaniline products. This method afforded an efficient protocol for the construct C-S and C-I bonds from the C-H bond under mild reaction conditions.