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

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.