Selective Oxidations of Organoboron Compounds Catalyzed by Baeyer–Villiger Monooxygenases

Abstract

AbstractThe applicability of Baeyer–Villiger monooxygenases (BVMOs) in organoboron chemistry has been explored through testing chemo‐ and enantioselective oxidations of a variety of boron‐containing aromatic and vinylic compounds. Several BVMOs, namely: phenylacetone monooxygenase (PAMO), M446G PAMO mutant, 4‐hydroxyacetophenone monooxygenase (HAPMO) and cyclohexanone monooxygenase (CHMO) were used in this study. The degree of chemoselectivity depends on the type of BVMO employed, in which the biocatalysts prefer boron‐carbon oxidation over Baeyer–Villiger oxidation or epoxidation. Interestingly, it was discovered that PAMO can be used to perform kinetic resolution of boron‐containing compounds with good enantioselectivities. These findings extend the known biocatalytic repertoire of BVMOs by showing a new family of compounds that can be oxidized by these enzymes.