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


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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Fig. 1: Photochemical water oxidation generating H2O2 to promote peroxygenase-catalysed hydroxylations.
Fig. 2: Time courses of the photoenzymatic hydroxylation of ethyl benzene at varying catalyst concentrations.
Fig. 3: Stability of rAaeUPO in the presence of anatase-Au-TiO2.
Fig. 4: EPR spectra recorded during the illumination of anatase and rutile Au-TiO2 in water.
Fig. 5: Effect of reducing the interaction of rAaeUPO with the TiO2 surface on the robustness of the photoenzymatic reaction.
Fig. 6: Photoenzymatic cascade reactions.
Fig. 7: Photoenzymatic halogenation of thymol.
Fig. 8: Photoenzymatic reactions using CND photocatalysts and FMN cocatalysts.


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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




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.

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Correspondence to Frank Hollmann.

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

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Zhang, W., Fernández-Fueyo, E., Ni, Y. et al. Selective aerobic oxidation reactions using a combination of photocatalytic water oxidation and enzymatic oxyfunctionalizations. Nat Catal 1, 55–62 (2018).

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