title: Peroxygenase-Catalyzed Oxyfunctionalization Reactions Promoted by the Complete Oxidation of Methanol.
abstract: Peroxygenases catalyze a broad range of (stereo)selective oxyfunctionalization reactions. However, to access their full catalytic potential, peroxygenases need a balanced provision of hydrogen peroxide to achieve high catalytic activity while minimizing oxidative inactivation. Herein, we report an enzymatic cascade process that employs methanol as a sacrificial electron donor for the reductive activation of molecular oxygen. Full oxidation of methanol is achieved, generating three equivalents of hydrogen peroxide that can be used completely for the stereoselective hydroxylation of ethylbenzene as a model reaction. Overall we propose and demonstrate an atom-efficient and easily applicable alternative to established hydrogen peroxide generation methods, which enables the efficient use of peroxygenases for oxyfunctionalization reactions.
authors.affiliation: Department of Biotechnology, Delft University of Technology, Julianalaan 136, 2628BL Delft (The Netherlands).
authors.forename: Yan
authors.initials: Y
authors.lastname: Ni
authors.affiliation: Department of Biotechnology, Delft University of Technology, Julianalaan 136, 2628BL Delft (The Netherlands).
authors.forename: Elena
authors.initials: E
authors.lastname: Fernández-Fueyo
authors.affiliation: Department of Biotechnology, Delft University of Technology, Julianalaan 136, 2628BL Delft (The Netherlands).
authors.forename: Alvaro
authors.initials: A
authors.lastname: Gomez Baraibar
authors.affiliation: Department of Bio- and Environmental Science, Technical University of Dresden-International Institute Zittau, 02763 Zittau (Germany).
authors.forename: René
authors.initials: R
authors.lastname: Ullrich
authors.affiliation: Department of Bio- and Environmental Science, Technical University of Dresden-International Institute Zittau, 02763 Zittau (Germany).
authors.forename: Martin
authors.initials: M
authors.lastname: Hofrichter
authors.affiliation: Department of Chemistry and Biotechnology, Graduate School of Engineering, Tottori University, 4-101 Koyamacho-Minami, Tottori, Tottori 680-8552 (Japan).
authors.forename: Hideshi
authors.initials: H
authors.lastname: Yanase
authors.affiliation: Department of Biocatalysis, Institute of Catalysis, CSIC, 28049 Madrid (Spain).
authors.forename: Miguel
authors.initials: M
authors.lastname: Alcalde
authors.affiliation: Laboratory of Biochemistry, Wageningen University, Dreijenlaan 3, 6703 HA Wageningen (The Netherlands).
authors.forename: Willem J H
authors.initials: WJ
authors.lastname: van Berkel
authors.affiliation: Department of Biotechnology, Delft University of Technology, Julianalaan 136, 2628BL Delft (The Netherlands). f.hollmann@tudelft.nl.
authors.forename: Frank
authors.initials: F
authors.lastname: Hollmann
mesh_terms: D002384:Catalysis; D000432:Methanol / Q000737:chemistry*; D006899:Mixed Function Oxygenases / Q000378:metabolism*; D010084:Oxidation-Reduction
chemical_list: D006899:Mixed Function Oxygenases; C022333:peroxygenase; D000432:Methanol
keywords: heme proteins; hydrogen peroxide; hydroxylation; oxidation; peroxygenases