Exploring the Temperature Effect on Enantioselectivity of a Baeyer‐Villiger Biooxidation by the 2, 5‐DKCMO Module: The SLM Approach. (16th June 2022)

• Record Type: Journal Article
• Authors: Röllig, Robert; Paul, Caroline E.; Duquesne, Katia; Kara, Selin; Alphand, Véronique
• Is Part Of: Chembiochem. Volume 23:Number 15(2022)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2022-06-16
• Subjects: chemoenzymatic Baeyer-Villiger oxidation -- kinetic resolution -- Shape Language Modeling -- temperature-dependent enantioselectivity; Biochemistry -- Periodicals; Molecular biology -- Periodicals; Pharmaceutical chemistry -- Periodicals; 572
• DOI: 10.1002/cbic.202200293
• Languages: English
• ISSNs: 1439-4227

Abstract

Abstract: Temperature is a crucial parameter for biological and chemical processes. Its effect on enzymatically catalysed reactions has been known for decades, and stereo‐ and enantiopreference are often temperature‐dependent. For the first time, we present the temperature effect on the Baeyer‐Villiger oxidation of rac‐ bicyclo[3.2.0]hept‐2‐en‐6‐one by the type II Bayer‐Villiger monooxygenase, 2, 5‐DKCMO. In the absence of a reductase and driven by the hydride‐donation of a synthetic nicotinamide analogue, the clear trend for a decreasing enantioselectivity at higher temperatures was observed. "Traditional" approaches such as the determination of the enantiomeric ratio ( E ) appeared unsuitable due to the complexity of the system. To quantify the trend, we chose to use the 'Shape Language Modelling' (SLM), a tool that allows the reaction to be described at all points in a shape prescriptive manner. Thus, without knowing the equation of the reaction, the substrate ee can be estimated that at any conversion. Abstract : Because the kinetic data did not fit with the usual model of the enantiomeric ratio, E, we used 'Shape Language Modeling' (SLM) – a shape prescriptive approach which does not requires a fixed mechanistic‐mathematical model ‐ to compare the effect of temperature (from 10 °C to 40 °C), on the enantioselectivity of Baeyer‐Villiger oxidation by a type II BVMO.