Catalyst Control over Regio- and Enantioselectivity in Baeyer–Villiger Oxidations of Functionalized Ketones

[Image: see text] We report a peptide-based catalyst that can strongly influence the regio- and enantioselectivity of the Baeyer–Villiger (BV) oxidation of cyclic ketones bearing amide, urea, or sulfonamide functional groups. Both types of selectivity are thought to arise from a catalyst–substrate hydrogen-bonding interaction. Furthermore, in selected cases, the reactions exhibit the hallmarks of parallel kinetic resolution. The capacity to use catalysis to select between BV products during an asymmetric process may have broad utility for both the synthesis and diversification of complex molecules, including natural products.