Peroxygenase-catalyzed oxyfunctionalization reactions promoted by the complete oxidation of methanol

Peroxygenase-catalyzed oxyfunctionalization reactions promoted by the complete oxidation of methanol

Ni, Y. (TU Delft BT/Biocatalysis)
Fernandez Fueyo, E. (TU Delft BT/Biocatalysis)
Baraibar, AG (External organisation)
Ullrich, R (Technische Universität Dresden)
Hofrichter, Martin (Technische Universität Dresden)
Yanase, H (Tottori University)
Alcalde, Miguel (University of the Balearic Islands)
van Berkel, WJH (Wageningen University & Research)
Hollmann, F. (TU Delft BT/Biocatalysis)

2016

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.

http://resolver.tudelft.nl/uuid:1b9f47f5-6085-4f95-aede-27745dca547b

https://doi.org/10.1002/anie.201507881

1433-7851

Angewandte Chemie (International Edition), 55 (2), 798-801

Accepted Author Manuscript. Title differs from the published version (version of record).

Institutional Repository

journal article

© 2016 Y. Ni, E. Fernandez Fueyo, AG Baraibar, R Ullrich, Martin Hofrichter, H Yanase, Miguel Alcalde, WJH van Berkel, F. Hollmann