Iwase Sadanobu, Inagi Shinsuke, Fuchigami Toshio
Department of Electronic Chemistry, Tokyo Institute of Technology, Yokohama 226-8502, Japan.
Department of Chemical Science and Engineering, Tokyo Institute of Technology, Yokohama 226-8502, Japan.
Beilstein J Org Chem. 2022 Jul 20;18:872-880. doi: 10.3762/bjoc.18.88. eCollection 2022.
The cathodic reduction of bromodifluoromethyl phenyl sulfide () using -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 with SmI resulted in much lower product yields. The detailed reaction mechanism was clarified based on the cathodic reduction of in the presence of deuterated acetonitrile, CDCN.
以邻苯二甲腈作为介质，对溴二氟甲基苯硫醚（）进行阴极还原，生成（苯硫基）二氟甲基自由基，该自由基分别与α-甲基苯乙烯和1,1-二苯乙烯反应，以中等产率和高产率得到相应的加合物。相比之下，用二碘化钐对进行化学还原，产物产率要低得多。基于在氘代乙腈CDCN存在下对的阴极还原，阐明了详细的反应机理。
