Photochemically Produced Aminocyclobutanes as Masked Dienes in Thermal Electrocyclic Cascade Reactions.

Cyclobutane products of a triplet sensitized enamide-alkene intramolecular [2 + 2] photocycloaddition have been shown to undergo fragmentation under acidic conditions. This lability has been exploited by inducing a complexity-generating thermal electrocyclic cascade sequence involving the in situ formation of a cyclobutene, followed by electrocyclic ring opening, Diels-Alder cycloaddition, and subsequent lactamization. This combination of excited state photochemistry and thermal electrocyclic cascade reactions allows simple planar molecules to be rapidly transformed into sp-rich scaffolds.