Divergent dehydroxyfluorination and carbonation of alcohols with trifluoromethyl trifluoromethanesulfonate

Preparation of alkyl fluorides and carbonates via divergent dehydroxyfluorination and carbonation of alcohols with trifluoromethyl trifluoromethanesulfonate (CF 3 SO 2 OCF 3 ) is described. The reactions performed with BTMG in THF provided alkyl fluorides in good yields, whereas those of two different alcohols with Et 3 N in DCM formed asymmetric carbonates in moderate to excellent yields. CF 3 SO 2 OCF 3 was demonstrated to be either a "F" or a "CO" reagent in the reactions by changing the base, allowing the selective construction of alkyl fluorides and carbonates from the corresponding alcohols with high efficiency. Notably, the fluorine-containing asymmetric carbonates that are difficult to synthesize by other methods were comprehensively prepared by this method, which would have great application potential in both academic and industrial fields. CF 3 SO 2 OCF 3 was proved to be a useful "F"/"CO" reagent in the selective preparation of alkyl fluorides and carbonates from alcohols by varying the bases.