Metal-Free Chemoselective ortho-C(sp2)–F Bond Hydroxylation and N-Trifluoroacylation of Fluoroarylamines for Domino Synthesis of 2-(N-Trifluoroacyl)aminophenols

A novel chemoselective reaction for the formation of C–O bonds by C(sp 2 )–F bond cleavage and concomitant N-trifluoroacylation of fluoroanilines using trifluoroacetic acid and Oxone ® is presented. This domino reaction gives o -hydroxy- N -trifluoroacetanilides in good yields under metal-free conditions in a single step. Selective ortho -directed monohydroxylation and N-trifluoroacylation of 2- and 6-fluoro- or 2,6-difluoro-substituted anilines takes place in this transformation.