An enantioselective hydroxylative dearomatization of 2-naphthols with oxaziridines has been accomplished using a N,N′-dioxide–scandium(III) complex catalyst. Various substituted ortho-quinols could be obtained in high yields (up to 99%) and enantioselectivities (up to 95 : 5 er). This methodology could be applied in the synthesis of bioactive lacinilenes in a gram-scale reaction. Based on the experimental investigations and previous work, a possible catalytic model was proposed.