Barber, Verity, Mielke, Tamara, Diaz-Rodriguez, Alba et al. (3 more authors) (2024) Unspecific Peroxygenase (UPO) can be Tuned for Oxygenation or Halogenation Activity by Controlling the Reaction pH. Chemistry : A European Journal. e2024017. ISSN 1521-3765
Abstract
Unspecific Peroxygenases (UPOs) are increasingly significant enzymes for selective oxygenations as they are stable, highly active and catalyze their reactions at the expense of only hydrogen peroxide as the oxidant. Their structural similarity to chloroperoxidase (CPO) means that UPOs can also catalyze halogenation reactions based upon the generation of hypohalous acids from halide and H2O2. Here we show that the halogenation and oxygenation modes of a UPO can be stimulated at different pH values. Using simple aromatic compounds such as thymol, we show that, at a pH of 3.0 and 6.0, either brominated or oxygenated products respectively are produced. Preparative 100 mg scale transformations of substrates were performed with 60–72% isolated yields of brominated products obtained. A one-pot bromination-oxygenation cascade reaction on 4-ethylanisole, in which the pH was adjusted from 3.0 to 6.0 at the halfway stage, yielded sequentially brominated and oxygenated products 1-(3-bromo-4-methoxyphenyl)ethyl alcohol and 3-bromo-4-methoxy acetophenone with 82% combined conversion. These results identify UPOs as an unusual example of a biocatalyst that is tunable for entirely different chemical reactions, dependent upon the reaction conditions.
Metadata
Item Type: | Article |
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Authors/Creators: |
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Copyright, Publisher and Additional Information: | © 2024 The Authors |
Dates: |
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Institution: | The University of York |
Academic Units: | The University of York > Faculty of Sciences (York) > Chemistry (York) |
Depositing User: | Pure (York) |
Date Deposited: | 23 May 2024 14:40 |
Last Modified: | 17 Nov 2024 00:50 |
Published Version: | https://doi.org/10.1002/chem.202401706 |
Status: | Published online |
Refereed: | Yes |
Identification Number: | 10.1002/chem.202401706 |
Open Archives Initiative ID (OAI ID): | oai:eprints.whiterose.ac.uk:212760 |
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Description: Chemistry A European J - 2024 - Barber - Unspecific Peroxygenase UPO can be Tuned for Oxygenation or Halogenation
Licence: CC-BY 2.5