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Updated: Oct 10, 2025

Protocol for the Synthesis of Ortho-trifluoromethoxylated Aniline Derivatives
Published on: January 19, 2016
Expeditious and Efficient ortho-Selective Trifluoromethane-sulfonylation of Arylhydroxylamines
Yue Liu1, Songlin Bai2,3, Yuanbo Du1
1School of Chemistry and Chemical Engineering, Shandong University, 27 South Shanda Road, Ji'nan, 250100, Shandong, China.
Abstract:
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.
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