Abstract The reaction of aromatic or benzylic disulfides with 2.5 equiv of Selectfluor™ in acetonitrile/water (10: 1) at room temperature efficiently produced the corresponding thiosulfonates. Conversely, the reaction of disulfides with 6.5 equiv of Selectfluor™ or thiosulfonates with 4.5 equiv of Selectfluor™ in refluxing acetonitrile/water (10: 1) provided sulfonyl fluorides in high yields. Accufluor™ and FP-T300™ are also effective in preparing ...