The stereoselective oxidation of benzoazepine-fused isoindolines to benzoazepine-fused isoindole atropodiastereomers is investigated, revealing a central-to-axial chirality conversion. By leveraging the characteristic folded conformation of these C-N atropisomers, Diels-Alder cycloaddition of the isoindole is achieved with complete facial selectivity, generating sp