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 I2 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.