One‐Pot Enantioselective Synthesis of 1,4‐Naphthoquinone‐Derived Polycycles through Oxidative Dearomatization and Aminocatalysis

Abstract

Abstract A synthetic process merging oxidative dearomatization and asymmetric aminocatalysis in a single vessel is reported. The PhI(OAc) 2 ‐mediated oxidation of 1,4‐dihydroxynaphthalene is followed by a trienamine‐mediated Diels–Alder cycloaddition/aldol reaction or a trienamine‐mediated Diels–Alder cycloaddition/oxidation sequence depending on the dienal substitution pattern. The polycyclic compounds are obtained in good yields with enantiomeric excesses up to 99 %. Additionally, these polycyclic architectures can be synthesized with similar enantioselectivities through an unprecedented one‐pot marriage of bodipy‐photocatalyzed oxidative dearomatization of 1‐naphthol and asymmetric aminocatalysis. A catalytic cycle is suggested to explain the reaction outcome.