Origins of Enhanced Enantioselectivity in the Pd-Catalyzed Decarboxylative Allylic Alkylation of N-Benzoyl Lactams

We explore the origins of marked improvement in enantioselectivity inner-sphere (PHOX)Pd-catalyzed allylic alkylation N-benzoyl lactam nucleophiles over their carbocyclic counterparts. employ density functional theory calculations to aid interpretation experimental results. Ultimately, we propose that enhancement arises primarily from noncovalent interactions between substrate and ligand rather than secondary chelation, as previously hypothesized.