A chiral all-carbon tetrasubstitutedVQM is generated by chiral phosphoric acid catalyzed nucleophilic addition of 2-alkynylnaphthols to o-quinone methides or imines, and it can be captured intramolecularly by a cycloaddition reaction. A wide range of naphthyl-2H-chromenes bearing axially and centrally chiral elements and axiallychiral quinone-naphthols were prepared efficiently with excellent enantioselectivities