Chromoselective Photocatalysis Enables Stereocomplementary Biocatalytic Pathways

Luca Schmermund; Susanne Reischauer; Sarah Bierbaumer; Christoph Winkler; Alba Diaz-Rodriguez; Lee Edwards; Selin Kara; Tamara Mielke; J.L. Cartwright; Gideon James Grogan; Bartholomaus Pieber; Wolfgang Kroutil

doi:10.1002/anie.202100164

Chromoselective Photocatalysis Enables Stereocomplementary Biocatalytic Pathways

Luca Schmermund, Susanne Reischauer, Sarah Bierbaumer, Christoph Winkler, Alba Diaz-Rodriguez, Lee Edwards, Selin Kara, Tamara Mielke, J.L. Cartwright, Gideon James Grogan, Bartholomaus Pieber, Wolfgang Kroutil

Chemistry

Research output: Contribution to journal › Article › peer-review

Abstract

Controlling the selectivity of a chemical reaction with
external stimuli is common in thermal processes, but rare in visible light photocatalysis. Here we show that the redox potential of a carbon nitride photocatalyst (CN-OA-m) can be tuned by changing the irradiation wavelength to generate electron holes with different
oxidation potentials. This tuning was the key to realizing photochemo-enzymatic cascades that give either the (S)- or the (R)-
enantiomer of phenylethanol. In combination with an unspecific
peroxygenase from Agrocybe aegerita, green light irradiation of CNOA-m led to the enantioselective hydroxylation of ethylbenzene to (R)-1-phenylethanol (99% e.e.). In contrast, blue light irradiation triggered the photocatalytic oxidation of ethylbenzene to acetophenone, which in turn was enantioselectively reduced with an alcohol dehydrogenase from Rhodococcus ruber to form (S)-1-phenylethanol (93% e.e.).

Original language	English
Journal	Angewandte Chemie International Edition
Volume	60
Issue number	13
Early online date	2 Feb 2021
DOIs	https://doi.org/10.1002/anie.202100164
Publication status	Published - 22 Mar 2022

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anie.202100164
© 2021 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH
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Cite this

@article{ca5528160900479f80729d5ea44571a8,

title = "Chromoselective Photocatalysis Enables Stereocomplementary Biocatalytic Pathways",

abstract = "Controlling the selectivity of a chemical reaction withexternal stimuli is common in thermal processes, but rare in visible light photocatalysis. Here we show that the redox potential of a carbon nitride photocatalyst (CN-OA-m) can be tuned by changing the irradiation wavelength to generate electron holes with differentoxidation potentials. This tuning was the key to realizing photochemo-enzymatic cascades that give either the (S)- or the (R)-enantiomer of phenylethanol. In combination with an unspecificperoxygenase from Agrocybe aegerita, green light irradiation of CNOA-m led to the enantioselective hydroxylation of ethylbenzene to (R)-1-phenylethanol (99% e.e.). In contrast, blue light irradiation triggered the photocatalytic oxidation of ethylbenzene to acetophenone, which in turn was enantioselectively reduced with an alcohol dehydrogenase from Rhodococcus ruber to form (S)-1-phenylethanol (93% e.e.).",

author = "Luca Schmermund and Susanne Reischauer and Sarah Bierbaumer and Christoph Winkler and Alba Diaz-Rodriguez and Lee Edwards and Selin Kara and Tamara Mielke and J.L. Cartwright and Grogan, {Gideon James} and Bartholomaus Pieber and Wolfgang Kroutil",

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T1 - Chromoselective Photocatalysis Enables Stereocomplementary Biocatalytic Pathways

AU - Schmermund, Luca

AU - Reischauer, Susanne

AU - Bierbaumer, Sarah

AU - Winkler, Christoph

AU - Diaz-Rodriguez, Alba

AU - Edwards, Lee

AU - Kara, Selin

AU - Mielke, Tamara

AU - Cartwright, J.L.

AU - Grogan, Gideon James

AU - Pieber, Bartholomaus

AU - Kroutil, Wolfgang

PY - 2022/3/22

Y1 - 2022/3/22

N2 - Controlling the selectivity of a chemical reaction withexternal stimuli is common in thermal processes, but rare in visible light photocatalysis. Here we show that the redox potential of a carbon nitride photocatalyst (CN-OA-m) can be tuned by changing the irradiation wavelength to generate electron holes with differentoxidation potentials. This tuning was the key to realizing photochemo-enzymatic cascades that give either the (S)- or the (R)-enantiomer of phenylethanol. In combination with an unspecificperoxygenase from Agrocybe aegerita, green light irradiation of CNOA-m led to the enantioselective hydroxylation of ethylbenzene to (R)-1-phenylethanol (99% e.e.). In contrast, blue light irradiation triggered the photocatalytic oxidation of ethylbenzene to acetophenone, which in turn was enantioselectively reduced with an alcohol dehydrogenase from Rhodococcus ruber to form (S)-1-phenylethanol (93% e.e.).

AB - Controlling the selectivity of a chemical reaction withexternal stimuli is common in thermal processes, but rare in visible light photocatalysis. Here we show that the redox potential of a carbon nitride photocatalyst (CN-OA-m) can be tuned by changing the irradiation wavelength to generate electron holes with differentoxidation potentials. This tuning was the key to realizing photochemo-enzymatic cascades that give either the (S)- or the (R)-enantiomer of phenylethanol. In combination with an unspecificperoxygenase from Agrocybe aegerita, green light irradiation of CNOA-m led to the enantioselective hydroxylation of ethylbenzene to (R)-1-phenylethanol (99% e.e.). In contrast, blue light irradiation triggered the photocatalytic oxidation of ethylbenzene to acetophenone, which in turn was enantioselectively reduced with an alcohol dehydrogenase from Rhodococcus ruber to form (S)-1-phenylethanol (93% e.e.).

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