Chromoselective Photocatalysis Enables Stereocomplementary Biocatalytic Pathways

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 electro...

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Bibliographic Details
Published in:Angewandte Chemie 2021-03, Vol.133 (13), p.7041-7045
Main Authors: Schmermund, Luca, Reischauer, Susanne, Bierbaumer, Sarah, Winkler, Christoph K., Diaz‐Rodriguez, Alba, Edwards, Lee J., Kara, Selin, Mielke, Tamara, Cartwright, Jared, Grogan, Gideon, Pieber, Bartholomäus, Kroutil, Wolfgang
Format: Article
Language:English
Subjects:
Acetophenone
Alcohol dehydrogenase
Carbon nitride
carbon nitrides
Chemical reactions
Chemistry
chromoselectivity
C−H activation
Enantiomers
Ethylbenzene
External stimuli
Holes (electron deficiencies)
Hydroxylation
Irradiation
Light irradiation
Oxidation
photobiocatalysis
Photocatalysis
Photooxidation
Radiation
Redox potential
Rhodococcus
Selectivity
unspecific peroxygenases
Zuschrift
Zuschriften
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Summary: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). Green or blue? The wavelength controls the outcome. Chromoselective activation of a carbon nitride generates electron holes with different oxidation potentials that are used for selective oxidation processes. By coupling the photocatalytic reactions with biocatalysis the (S)‐ or the (R)‐enantiomer of 1‐phenylethanol was synthesized stereoselectively.
ISSN:0044-8249
1521-3757
DOI:10.1002/ange.202100164