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Chromoselective Photocatalysis Enables Stereocomplementary Biocatalytic Pathways **
Author(s) -
Schmermund Luca,
Reischauer Susanne,
Bierbaumer Sarah,
Winkler Christoph K.,
DiazRodriguez Alba,
Edwards Lee J.,
Kara Selin,
Mielke Tamara,
Cartwright Jared,
Grogan Gideon,
Pieber Bartholomäus,
Kroutil Wolfgang
Publication year - 2021
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.202100164
Subject(s) - photocatalysis , acetophenone , chemistry , ethylbenzene , photochemistry , biocatalysis , hydroxylation , redox , enantioselective synthesis , enantiomer , selectivity , alcohol dehydrogenase , irradiation , combinatorial chemistry , organic chemistry , enzyme , reaction mechanism , benzene , catalysis , physics , nuclear physics
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 ).