Alkyl-, haloalkyl-, and ketoalkyl-2-ethoxycarbonyl-1, 3-dithianes were easily made from the appropriate primary or secondary alkyl bromides, 1, 3-dithiane, and ethyl chloroformate. They were reacted with BrF3 to form the corresponding α, α-difluoro esters in 65-75% yield. Reaction conditions are very mild (1-2 min, 0° C). The two sulfur atoms of the dithiane are essential for the reaction.