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Selective aerobic oxidation reactions using a combination of photocatalytic water oxidation and enzymatic oxyfunctionalizations

Nature Catalysisvolume 1pages5562 (2018) | Download Citation


Peroxygenases offer an attractive means to address challenges in selective oxyfunctionalization chemistry. Despite this, their application in synthetic chemistry remains challenging due to their facile inactivation by the stoichiometric oxidant H2O2. Often atom-inefficient peroxide generation systems are required, which show little potential for large-scale implementation. Here, we show that visible-light-driven, catalytic water oxidation can be used for in situ generation of H2O2 from water, rendering the peroxygenase catalytically active. In this way, the stereoselective oxyfunctionalization of hydrocarbons can be achieved by simply using the catalytic system, water and visible light.

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Financial support by the European Research Council (ERC Consolidator grant no. 648026) is gratefully acknowledged. The authors thank B. Norder for XRD, W. H. Evers for TEM and F. Hagen for EPR measurements. The authors also thank S. Schmidt for the preparation of benzaldehyde lyase, M. Pesic for the preparation of YqjM and T. Knaus for the preparation of ω-transaminases. F.G.M. received funding as an ERC Starting Grant Fellow (grant agreement 638271).

Author information


  1. Department of Biotechnology, Delft University of Technology, Delft, The Netherlands

    • Wuyuan Zhang
    • , Elena Fernández-Fueyo
    • , Yan Ni
    • , Morten van Schie
    • , Jenö Gacs
    •  & Frank Hollmann
  2. Van’t Hoff Institute for Molecular Sciences (HIMS), Faculty of Science, University of Amsterdam, Amsterdam, The Netherlands

    • Rokus Renirie
    • , Ron Wever
    •  & Francesco G. Mutti
  3. Institute of Bio- and Geosciences, IBG-1: Biotechnology, Forschungszentrum Jülich GmbH, Jülich, Germany

    • Dörte Rother
  4. Department of Biocatalysis, Institute of Catalysis, CSIC, Madrid, Spain

    • Miguel Alcalde


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W.Z., E.F.-F., Y.N., M.v.S. and J.G. performed the experimental work and analysed the results; R.R., R.W., F.G.M., D.R. and M.A. provided biocatalysts and participated in the planning and analysis of the experiments; W.Z. and F.H. conceived and designed the experiments. All authors co-wrote the manuscript.

Competing interests

The authors declare no competing financial interests.

Corresponding author

Correspondence to Frank Hollmann.

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    Supplementary Methods, Supplementary Figures 1-37, Supplementary Tables 1-5, Supplementary References.

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