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 (CF3SO2OCF3) is described. The reactions performed with BTMG in THF provided alkyl fluorides in good yields, whereas those of two different alcohols with Et3N in DCM formed asymmetric carbonates in moderate to excellent yields. CF3SO2OCF3 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.