biostudies-literatureSchmermund LAustrian Science Fund FWFDeutsche ForschungsgemeinschaftHorizon 2020 Framework Programme7041-7045https://www.ebi.ac.uk/biostudies/studies/S-EPMC10946972biostudies-literatureUnknown133(13)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 (<i>S</i>)- or the (<i>R</i>)-enantiomer of phenylethanol. In combination with an unspecific peroxygenase from <i>Agrocybe aegerita</i>, green light irradiation of CN-OA-m led to the enantioselective hydroxylation of ethylbenzene to (<i>R</i>)-1-phenylethanol (99 % <i>ee</i>). In contrast, blue light irradiation triggered the photocatalytic oxidation of ethylbenzene to acetophenone, which in turn was enantioselectively reduced with an alcohol dehydrogenase from <i>Rhodococcus ruber</i> to form (<i>S</i>)-1-phenylethanol (93 % <i>ee</i>).Angewandte Chemie (Weinheim an der Bergstrasse, Germany)Chromoselective Photocatalysis Enables Stereocomplementary Biocatalytic Pathways.PMC10946972EXC 2008 - 390540038764920DOC 46-B21Kroutil WReischauer SMielke TCartwright JSchmermund LBierbaumer SEdwards LJGrogan GWinkler CKDiaz-Rodriguez AKara SPieber BfalseChromoselective 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 electron holes with different oxidation potentials. This tuning was the key to realizing photo-chemo-enzymatic cascades that give either the (<i>S</i>)- or the (<i>R</i>)-enantiomer of phenylethanol. In combination with an unspecific peroxygenase from <i>Agrocybe aegerita</i>, green light irradiation of CN-OA-m led to the enantioselective hydroxylation of ethylbenzene to (<i>R</i>)-1-phenylethanol (99 % <i>ee</i>). In contrast, blue light irradiation triggered the photocatalytic oxidation of ethylbenzene to acetophenone, which in turn was enantioselectively reduced with an alcohol dehydrogenase from <i>Rhodococcus ruber</i> to form (<i>S</i>)-1-phenylethanol (93 % <i>ee</i>).2021-01-01T00:00:00Z2021 Mar2025-04-26T12:08:19.736Z2025-04-06T13:54:32.805ZS-EPMC109469723850495510.1002/ange.202100164