Fluoride-Catalyzed Fluoroacetylation of Alcohols, Thioalcohols, and Nitrogen-Containing Compounds

The strained C–N bond of fluoroacetamides was activated by fluoride to form acyl fluoride, thereby enabling mild O -, S -, N -fluoroacetylation. The reaction of alcohols, thioalcohols, and nitrogen-containing compounds with N -phenyl- N -tosylfluoroacetamides proceeded smoothly in the presence of a fluoride catalyst to provide α-fluorinated esters, thioesters, and amides in satisfactory to excellent yields at ambient temperature. The potential of this mild fluoroacetylation is highlighted by large-scale synthesis and late-stage diversification of chiral and medicinally relevant molecules.