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

Abstract

A novel palladium-catalyzed intermolecular ditrifluoromethoxylation of unactivated alkenes has been developed, using a new electrophilic reagent, Selectfluor^CN, 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.