Exploring the Temperature Effect on Enantioselectivity of a Baeyer-Villiger Biooxidation by the 2,5-DKCMO Module: The SLM Approach |
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Authors: | Robert Röllig Caroline E. Paul Katia Duquesne Selin Kara Véronique Alphand |
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Affiliation: | 1. Aix-Marseille Univ, CNRS, Centrale Marseille, iSm2 UMR CMRS 7313, Aix-Marseille Université, Pôle de l'Etoile Avenue Escadrille Normandie Niemen, 13397 Marseille, France;2. Department of Biotechnology, Delft University of Technology, Van der Maasweg 9, Delft, 2629 HZ The Netherlands;3. Biocatalysis and Bioprocessing Group, Department of Biological and Chemical Engineering, Aarhus University, Gustav Wieds Vej 10, Aarhus, 8000 Aarhus C Denmark |
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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. |
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Keywords: | chemoenzymatic Baeyer-Villiger oxidation kinetic resolution Shape Language Modeling temperature-dependent enantioselectivity |
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