Ancistrotectoquinones A and B, the First Quinoid Naphthylisoquinoline Alkaloids, from the Chinese Liana Ancistrocladus tectorius

Abstract

From the leaves and stems of Ancistrocladus tectorius (Ancistrocladaceae) from the Chinese island Hainan, two novel-type 7,3′-coupled naphthylisoquinolines, named ancistrotectoquinones A (4) and B (5), were isolated. They are the first alkaloids with a 1,4-naphthoquinone portion coupled to an isoquinoline moiety. Due to the lowered degree of steric hindrance next to the biaryl axis and for electronic reasons, 4 and 5 occur as pairs of configurationally semi-stable, and, thus slowly interconverting atropo-diastereomers. The Gibbs free energies of activation between the two atropisomers of ancistrotectoquinone A (4a/b) were determined by measuring the time-dependent decrease of diastereomeric purity of freshly separated samples enriched with the M- or P-atropisomer and, computationally, by DFT calculations. The absolute configurations at the biaryl axes of the atropo-diastereomers of 4a/b and 5a/b were assigned by online LC-CD analysis. The stereostructure of 4a/b was further confirmed by its semi-synthesis from the likewise 7,3′-coupled ‘normal' naphthylisoquinoline alkaloid ancistrotectorine (6), by biomimetic oxidation with Fremy's salt.