The hypervalent iodine/HF reagent consisting of PhIO and HF•py was found to be effective for fluorination of functionalized aromatic olefins bearing synthetically important carbonyl and hydroxyl groups. Fluorination of 1,3-diphenyl-2propen-1-one with PhIO/HF•py reagent in CH 2 Cl 2 at room temperature gave 3,3difluoro-1,2-diphenyl-1-propanone in high yield. Other α-aryl-α,β-unsaturated ketones underwent the fluorination to yield aryl 2,2-difluoroethyl ketone derivatives in good to high yields. Catalytic fluorination of α-aryl-α,β-unsaturated ketones using a p-TolI/HF•py/mCPBA reagent system also worked well. Moreover, the fluorination of cinnamyl alcohol derivatives by PhIO/HF•py reagent proceeded smoothly to afford 2-aryl-3,3-difluoro-1-propanols in moderate yields.

The intramolecular aminofluorination of homoallylamine derivatives using a reagent system of PhI(OAc) and Py·HF in CHCl at room temperature for 5 h gave N-tosyl-3-fluoropyrrolidines in good to high yields. Furthermore, the catalytic aminofluorination was furnished by the reaction using p-iodotoluene as a catalyst in the presence of Py·HF as a fluorine source and mCPBA as a terminal oxidant.