Skip to Main content Skip to Navigation
New interface
Journal articles

Divorce in the two-component BVMO family: the single oxygenase for enantioselective chemo-enzymatic Baeyer–Villiger oxidations

Abstract : Two-component flavoprotein monooxygenases consist of a reductase and an oxygenase enzyme. The proof of functionality of the latter without its counterpart as well as the mechanism of flavin transfer remains unanswered beyond doubt. To tackle this question, we utilized a reductase-free reaction system applying purified 2,5-diketocamphane-monooxygenase I (2,5-DKCMO), a FMN-dependent type II Baeyer-Villiger monooxygenase, and synthetic nicotinamide analogues (NCBs) as dihydropyridine derivatives for FMN reduction. This system demonstrated the stand-alone quality of the oxygenase, as well as the mechanism of FMNH 2 transport by free diffusion. The efficiency of this reductase-free system strongly relies on the balance of FMN reduction and enzymatic (re)oxidation, since reduced FMN in solution causes undesired side reactions, such as hydrogen peroxide formation. Design of experiments allowed us to (i) investigate the effect of various reaction parameters, underlining the importance to balance the FMN/FMNH 2 cycle, (ii) optimize the reaction system for the enzymatic Baeyer-Villiger oxidation of racbicyclo[3.2.0]hept-2-en-6-one, rac-camphor, and rac-norcamphor. Finally, this study not only demonstrates the reductase-independence of 2,5-DKCMO, but also revisits the terminology of two-component flavoprotein monooxygenases for this specific case. † Electronic supplementary information (ESI) available. See
Document type :
Journal articles
Complete list of metadata
Contributor : Patricia BREMOND Connect in order to contact the contributor
Submitted on : Wednesday, October 13, 2021 - 10:12:37 AM
Last modification on : Tuesday, September 13, 2022 - 4:29:11 PM
Long-term archiving on: : Friday, January 14, 2022 - 6:36:40 PM


Publication funded by an institution


Distributed under a Creative Commons Attribution - NonCommercial 4.0 International License



Robert Röllig, Caroline E Paul, Magalie Claeys-Bruno, Katia Duquesne, Selin Kara, et al.. Divorce in the two-component BVMO family: the single oxygenase for enantioselective chemo-enzymatic Baeyer–Villiger oxidations. Organic & Biomolecular Chemistry, 2021, 19 (15), pp.3441 - 3450. ⟨10.1039/d1ob00015b⟩. ⟨hal-03375863⟩



Record views


Files downloads