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

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.