Iodine(III)‐Mediated Electrophilic Chlorination and Catalytic Nitration of N‐Tosyl Anilines

Abstract An efficient iodine(III)‐based protocol for the chlorination and catalytic nitration of N ‐tosyl anilines as well as the proposed reaction mechanism is described. The synergistic combination of the commercially available [bis(trifluoroacetoxy)iodo]benzene (PIFA) with AlCl 3 , or (PhIO) n with Al(NO 3 ) 3 , allowed the electrophilic introduction of chlorine and nitro group in the N ‐tosyl aniline core in non‐acidic conditions. Our DFT calculations, performed for the chlorination process, indicate that this occurs through a cationic pathway in which the [Cl‐PhI OTFA⋅AlCl 3 ] is the chlorinating species and is formed under neutral conditions.