Highly Diastereoselective Palladium-Catalyzed Oxidative Cascade Carbonylative Carbocyclization of Enallenols

A palladium-catalyzed oxidative cascade carbonylative carbocyclization of enallenols was developed. Under mild reaction conditions, a range of cis-fused [5,5] bicyclic γ-lactones and γ-lactams with a 1,3-diene motif were obtained in good yields with high diastereoselectivity. The obtained lactone/lactam products are viable substrates for a stereoselective Diels–Alder reaction with N-phenylmaleimide, providing polycyclic compounds with increased molecular complexity.