An organocatalytic enantioselective aza-Friedel–Crafts addition of 2-naphthols to benzoxathiazine 2,2-dioxides is described using a quinine-derived bifunctional catalyst. The method allows the use of a wide range of aromatic compounds as nucleophiles, including 1-naphthol and sesamol, and benzoxathiazines 2,2-dioxides, expanding the existing state of the art enantioselective synthesis of aminomethylnaphthol derivatives.