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Updated: Jul 9, 2026

Protocol for the Synthesis of Ortho-trifluoromethoxylated Aniline Derivatives
Published on: January 19, 2016
Preparation and synthetic applications of aryl tetraflates (ArOSO2CF2CF2H)
Vsevolod V Rostovtsev1, Lois M Bryman, Christopher P Junk
1DuPont Central Research and Development, Experimental Station, Wilmington, Delaware 19880, USA. vsevolod.rostovtsev@usa.dupont.com
Abstract:
We have recently developed an improved synthetic route to 1,1,2,2-tetrafluoroethanesulfonic acid (HCF2CF2SO3H, TFESA) and explored the applications of this newly available superacid in catalysis. Low volatility, ease of handling, and a convenient 1H NMR handle make this acid an attractive alternative to triflic acid. TFESA can also be converted to several of its derivatives: anhydride, sulfonyl chloride, and sulfonyl fluoride, which provide a good entry point for the synthesis of aryl sulfonates. We prepared several aryl esters of 1,1,2,2-tetrafluoroethanesulfonic acid (aryl tetraflates) and showed that they can be used in a number of palladium-catalyzed coupling reactions (Suzuki, Heck, and Buchwald-Hartwig couplings). While the reactivity of tetraflates lies between that of triflates and chlorides, tetraflates appear to be more thermally stable. Additionally, the presence of a hydrogen atom in the tetraflate group facilitates monitoring of reactions and characterization of derivatives.
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