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.本研究开发了一种新型钯催化未活化烯烃的分子间双三氟甲氧基化反应，以新型亲电试剂SelectfluorCN作为强氧化剂，AgOCF3作为三氟甲氧基源。初步机理研究显示，该反应可能由Pd(IV)物种引发，CF3O–Pd(IV)对双键的非常规顺式加成生成首个C–OCF3键；此外，第二个C–OCF3键通过高价钯中心的还原消除过程形成。