Mechanistic Insights for Aniline‐Catalyzed Halogenation Reactions

Lewis base catalyzed electrophilic aromatic halogenation using N ‐halosuccinimides (NsX; X=Cl, Br, I) under mild conditions has attracted much attention, but the detailed mechanism remains elusive. Using the aniline MesNH 2 and anisole PhOMe as the typical base catalyst and aromatic substrate, respectively, a novel mechanism is revealed by extensive DFT calculations. The autogenic protonation of imine XMes=NH (via Mes=NH + mediated dimerization...