Pd-Catalyzed Cascade Reactions of Aziridines: One-Step Access to Complex Tetracyclic Amines

The combination of palladium catalysis and thermal cycloaddition is shown to transform tricyclic aziridines into complex, stereodefined tetracyclic products in a single step. This highly unusual cascade process involves diverted Tsuji–Trost sequence leading surprisingly facile intramolecular Diels–Alder reaction. starting materials are accessible on multigram scales from the photochemical rearrangement simple pyrroles. amine can be further elaborated through routine transformations, highlighting their potential as scaffolds for medicinal chemistry.