Two enantiocomplementary Baeyer-Villiger monooxygenases newly identified for asymmetric oxyfunctionalization of thioether

Two enantiocomplementary Baeyer-Villiger monooxygenases RaBVMO and AmBVMO were identified by genome mining for the asymmetric sulfoxidation. Both recombinant BVMOs have optimal pH of 9.0 and temperature of 35 degrees C. The half-lives of RaBVMO and AmBVMO at 30 degrees C were 24.4 and 24.6 h. RaBVMO and AmBVMO exhibited broad substrate spectrum and could catalyze the oxidization of various compounds including fatty ketones, cyclic ketones, and thioethers. Kinetic parameters analysis revealed that both RaBVMO and AmBVMO displayed higher catalytic efficiency toward thioanisole than cyclohexanone. As much as 50 mM thioanisole could be completely oxidized by AmBVMO and RaBVMO with 99% (R) and 95% (S), respectively. Molecular docking analysis further provides evidence for the complementary enantioselectivity of RaBVMO and AmBVMO. Our results demonstrate the potential application of the two novel BVMOs in asymmetric synthesis of sulfoxides.

Automated summary

Two enantiocomplementary Baeyer-Villiger monooxygenases, RaBVMO and AmBVMO, have been identified for asymmetric sulfoxidation with optimal pH of 9.0 and temperature of 35 degrees C. Both enzymes exhibit broad substrate spectrum and high catalytic efficiency, showing potential application in asymmetric synthesis of sulfoxides.