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

Abstract

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 SmI2 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, CD3CN.

Keywords

• bis(phenylthio)difluoromethane
• cathodic reduction
• deuteration
• o-phthalonitrile mediator
• (phenylthio)difluoromethylation
• (phenylthio)difluoromethyl radical