Exploring the Temperature Effect on Enantioselectivity of a Baeyer-Villiger Biooxidation by the 2,5-DKCMO Module

Exploring the Temperature Effect on Enantioselectivity of a Baeyer-Villiger Biooxidation by the 2,5-DKCMO Module: The SLM Approach

Röllig, Robert (Aarhus University; Aix Marseille Université)
Paul, C.E. (TU Delft BT/Biocatalysis)
Duquesne, Katia (Aix Marseille Université)
Kara, Selin (Aarhus University)
Alphand, Véronique (Aix Marseille Université)

2022

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.

chemoenzymatic Baeyer-Villiger oxidation
kinetic resolution
Shape Language Modeling
temperature-dependent enantioselectivity

http://resolver.tudelft.nl/uuid:d8cff151-7981-4232-aac3-b65e5a1b571b

https://doi.org/10.1002/cbic.202200293

1439-4227

ChemBioChem: a European journal of chemical biology, 23 (15)

Institutional Repository

journal article

© 2022 Robert Röllig, C.E. Paul, Katia Duquesne, Selin Kara, Véronique Alphand