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.