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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
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.202100164
Subject(s) - photocatalysis , chemistry , acetophenone , biocatalysis , photochemistry , ethylbenzene , enantiomer , redox , graphitic carbon nitride , enantioselective synthesis , enantiomeric excess , organic chemistry , reaction mechanism , catalysis
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 ).