SelectfluorTM‐Mediated Tandem Fluorination and 1,3‐Carbonyl Migration in ortho‐Carbonyl Anilines: Charge‐Transfer‐Enabled ortho‐Selectivity

Abstract

AbstractAn unprecedented tandem ortho‐selective fluorination and 1,3‐carbonyl migration in ortho‐carbonyl anilines using selectfluorTM as the sole reagent is reported. The reaction is transition‐metal free, does not require any pre‐functionalization, takes place under ambient conditions, and yields ortho‐fluoroanilide derivatives in moderate to good yields. SelectfluorTM serves the dual purpose of fluorine source and assists 1,3‐carbonyl migration. The formation of proposed charge transfer (CT) complex between ortho‐carbonyl aniline (donor) and selectfluorTM (acceptor), and its role in enabling the observed ortho‐selectivity is supported by experimental and computational investigations. The single‐electron‐transfer (SET) in the complex results in the formation of (2‐amino‐3‐fluorophenyl)(phenyl)methanone intermediate, which on subsequent 1,3‐carbonyl migration forms ortho‐fluoroanilide in presence of F+ or in‐situ generated H+.