Expeditious and Efficient ortho‐Selective Trifluoromethane‐sulfonylation of Arylhydroxylamines

A metal- and oxidant-free, practical and efficient method for the synthesis of highly versatile and synthetically useful ortho-trifluoromethanesulfonylated anilines from arylhydroxylamines and trifluoromethanesulfinic chloride was developed. This rapid transformation proceeded smoothly with good yields and excellent ortho-selectivity in the absence of any metals or ligands. Mechanistically, the reaction comprised a noncanonical O-trifluoromethanesulfinylation of the arylhydroxylamine, and the subsequent [2,3]-sigmatropic rearrangement to afford ortho-trifluoromethanesulfonylated aniline derivatives. The practical application of this reaction was demonstrated by further conversion into a series of functional molecules under different reaction conditions.