Polyenolate-mediated reaction cascade initiated by higher-order-cycloaddition for the construction of polycarbocyclic scaffolds

Abstract

In this manuscript, the application of polyenolate chemistry for the activation of higherenes towards a higher-order-cycloaddition-initiated cascade reaction is demonstrated. This has been made possible by using alkylidenemalononitriles derived from indene-2-carbaldehydes as the higherene precursors. Their reaction with an iminium ion, generated in situ in the presence of a suitable amino catalyst, allowed for a cascade reaction involving [10 + 2]-higher-order cycloaddition followed by Michael addition and aldol condensation to proceed in a highly stereoselective fashion.