1. Chromoselective Photocatalysis Enables Stereocomplementary Biocatalytic Pathways*.
- Author
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Schmermund L, Reischauer S, Bierbaumer S, Winkler CK, Diaz-Rodriguez A, Edwards LJ, Kara S, Mielke T, Cartwright J, Grogan G, Pieber B, and Kroutil W
- Subjects
- Acetophenones metabolism, Agrocybe enzymology, Alcohol Dehydrogenase metabolism, Benzene Derivatives metabolism, Catalysis, Light, Mixed Function Oxygenases metabolism, Molecular Structure, Nitriles metabolism, Oxidation-Reduction, Phenylethyl Alcohol metabolism, Photochemical Processes, Rhodococcus enzymology, Stereoisomerism, Acetophenones chemistry, Alcohol Dehydrogenase chemistry, Benzene Derivatives chemistry, Mixed Function Oxygenases chemistry, Nitriles chemistry, Phenylethyl Alcohol chemistry
- 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)., (© 2021 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)
- Published
- 2021
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