Palladium-Catalyzed Intermolecular Ditrifluoromethoxylation of Unactivated Alkenes: CF3O-Palladation Initiated by Pd(IV)

A novel palladium-catalyzed intermolecular ditrifluoromethoxylation of unactivated alkenes has been developed, using a new electrophilic reagent, SelectfluorCN, as a strong oxidant, and AgOCF3 as a trifluoromethoxide source. Preliminary mechanistic studies revealed that the reaction was possibly initiated by Pd(IV) species, and an unusual cis-addition of CF3O–Pd(IV) into the double bond leads to the formation of the first C–OCF3 bond; in addition, the second C–OCF3 bond was produced through reductive elimination at high-valent palladium center.