Toward Kilogram-Scale Peroxygenase-Catalyzed Oxyfunctionalization of Cyclohexane

Thomas Hilberath; Remco van Oosten; Juliet Victoria; Hugo Brasselet; Miguel Alcalde; John M Woodley; Frank Hollmann

doi:10.1021/acs.oprd.3c00135

Toward Kilogram-Scale Peroxygenase-Catalyzed Oxyfunctionalization of Cyclohexane

Org Process Res Dev. 2023 Jun 9;27(7):1384-1389. doi: 10.1021/acs.oprd.3c00135. eCollection 2023 Jul 21.

Authors

Thomas Hilberath¹, Remco van Oosten¹, Juliet Victoria², Hugo Brasselet³, Miguel Alcalde⁴, John M Woodley², Frank Hollmann¹

Affiliations

¹ Department of Biotechnology, Delft University of Technology, van der Maasweg 9, 2629HZ Delft, The Netherlands.
² Department of Chemical and Biochemical Engineering, Technical University of Denmark, 2800 Kgs. Lyngby, Denmark.
³ Atlant. Innov., Koornmarkt 52, 2611 EH Delft, The Netherlands.
⁴ Department of Biocatalysis, Institute of Catalysis, CSIC, 28049 Madrid, Spain.

Abstract

Mol-scale oxyfunctionalization of cyclohexane to cyclohexanol/cyclohexanone (KA-oil) using an unspecific peroxygenase is reported. Using AaeUPO from Agrocybe aegerita and simple H₂O₂ as an oxidant, cyclohexanol concentrations of more than 300 mM (>60% yield) at attractive productivities (157 mM h^-1, approx. 15 g L^-1 h^-1) were achieved. Current limitations of the proposed biooxidation system have been identified paving the way for future improvements and implementation.