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

Abstract An unprecedented tandem ortho‐ selective fluorination and 1,3‐carbonyl migration in ortho ‐carbonyl anilines using selectfluor TM 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. Selectfluor TM 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 selectfluor TM (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 + .