Cathodic generation of reactive (phenylthio)difluoromethyl species and its reactions: mechanistic aspects and synthetic applications.

The cathodic reduction of bromodifluoromethyl phenyl sulfide ( 1 ) using o -phthalonitrile as a mediator generated the (phenylthio)difluoromethyl radical, which reacted with α-methylstyrene and 1,1-diphenylethylene to provide the corresponding adducts in moderate and high yields, respectively. In contrast, chemical reduction of 1 with SmI 2 resulted in much lower product yields. The detailed reaction mechanism was clarified based on the cathodic reduction of 1 in the presence of deuterated acetonitrile, CD 3 CN.