Details
| Original language | English |
|---|---|
| Pages | 6965-6969 |
| Number of pages | 5 |
| Volume | 60 |
| Publication status | Published - 16 Mar 2021 |
| Externally published | Yes |
Publication series
| Name | Angewandte Chemie - International Edition |
|---|---|
| Publisher | John Wiley and Sons Ltd |
| ISSN (Print) | 1433-7851 |
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 photo-chemo-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 CN-OA-m led to the enantioselective hydroxylation of ethylbenzene to (R)-1-phenylethanol (99 % ee). 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 % ee).
Keywords
- carbon nitrides, chromoselectivity, C−H activation, photobiocatalysis, unspecific peroxygenases
ASJC Scopus subject areas
- Chemical Engineering(all)
- Catalysis
- Chemistry(all)
- General Chemistry
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13. ed. 2021. p. 6965-6969 (Angewandte Chemie - International Edition).
Research output: Working paper/Preprint › Working paper/Discussion paper
}
TY - UNPB
T1 - Switching Between Enantiomers by Combining Chromoselective Photocatalysis and Biocatalysis
AU - Schmermund, Luca
AU - Reischauer, Susanne
AU - Bierbaumer, Sarah
AU - Winkler, Christoph K.
AU - Diaz-Rodriguez, Alba
AU - Edwards, Lee J.
AU - Kara, Selin
AU - Mielke, Tamara
AU - Cartwright, Jared
AU - Grogan, Gideon
AU - Pieber, Bartholomäus
AU - Kroutil, Wolfgang
N1 - Funding Information: This project received funding from the European Union's Horizon 2020 research and innovation programme under the Marie Skłodowska‐Curie grant agreement No 764920. S.B. acknowledges the Austrian Science Fund (FWF) for funding within the project CATALOX (DOC 46‐B21). The University of Graz and the Field of Excellence BioHealth are acknowledged for financial support. We thank GlaxoSmithKline for providing the Photochemistry LED Illuminator (Pacer Components Ltd. Pangbourne, UK). S.R. and B.P. acknowledge the Max‐Planck Society and the German Chemical Industry Fund (Liebig Fellowship, Fonds der Chemischen Industrie, FCI) for generous financial support. B.P. thanks the Deutsche Forschungsgemeinschaft (DFG, German Research Foundation) under Germany's Excellence Strategy—EXC 2008–390540038—UniSysCat for financial support. T.M. was funded by a studentship awarded by the industrial affiliates of the Centre of Excellence for Biocatalysis, Biotransformations and Biomanufacture (CoEBio3). We thank Prof. Klaus Zangger and Bernd Werner for recording of NMR spectra.
PY - 2021/3/16
Y1 - 2021/3/16
N2 - 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 photo-chemo-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 CN-OA-m led to the enantioselective hydroxylation of ethylbenzene to (R)-1-phenylethanol (99 % ee). 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 % ee).
AB - 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 photo-chemo-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 CN-OA-m led to the enantioselective hydroxylation of ethylbenzene to (R)-1-phenylethanol (99 % ee). 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 % ee).
KW - carbon nitrides
KW - chromoselectivity
KW - C−H activation
KW - photobiocatalysis
KW - unspecific peroxygenases
UR - http://www.scopus.com/inward/record.url?scp=85101618129&partnerID=8YFLogxK
U2 - 10.26434/chemrxiv.13521527.v1
DO - 10.26434/chemrxiv.13521527.v1
M3 - Working paper/Discussion paper
C2 - 33529432
AN - SCOPUS:85101618129
VL - 60
T3 - Angewandte Chemie - International Edition
SP - 6965
EP - 6969
BT - Switching Between Enantiomers by Combining Chromoselective Photocatalysis and Biocatalysis
ER -