Origins of Enhanced Enantioselectivity in the Pd-Catalyzed Decarboxylative Allylic Alkylation of <em>N</em>-Benzoyl Lactams
Alexander Q. Cusumano,
Tianyi Zhang,
William A. Goddard,
Brian M. Stoltz
Affiliations
Alexander Q. Cusumano
The Warren and Katharine Schlinger Laboratory for Chemistry and Chemical Engineering, Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, CA 91125, USA
Tianyi Zhang
The Warren and Katharine Schlinger Laboratory for Chemistry and Chemical Engineering, Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, CA 91125, USA
William A. Goddard
Materials and Process Simulation Center, Beckman Institute, California Institute of Technology, Pasadena, CA 91125, USA
Brian M. Stoltz
The Warren and Katharine Schlinger Laboratory for Chemistry and Chemical Engineering, Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, CA 91125, USA
We explore the origins of the marked improvement in enantioselectivity in the inner-sphere (PHOX)Pd-catalyzed allylic alkylation of N-benzoyl lactam nucleophiles over their carbocyclic counterparts. We employ density functional theory calculations to aid in the interpretation of experimental results. Ultimately, we propose that the enhancement in enantioselectivity arises primarily from noncovalent interactions between the substrate and ligand rather than secondary substrate chelation, as previously hypothesized.
