Chromoselective Photocatalysis Enables Stereocomplementary Biocatalytic Pathways
| Autor: | Selin Kara, Jared Cartwright, Lee Edwards, Tamara Mielke, Bartholomäus Pieber, Wolfgang Kroutil, Luca Schmermund, Christoph K. Winkler, Alba Diaz-Rodriguez, Sarah Bierbaumer, Gideon Grogan, Susanne Reischauer |
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| Jazyk: | angličtina |
| Rok vydání: | 2021 |
| Předmět: |
Light
Photobiocatalysis 010402 general chemistry Photochemistry 01 natural sciences Redox Ethylbenzene C−H activation Catalysis Mixed Function Oxygenases chromoselectivity Hydroxylation chemistry.chemical_compound unspecific peroxygenases Unspecific peroxygenase Nitriles Agrocybe Benzene Derivatives Rhodococcus carbon nitrides Molecular Structure 010405 organic chemistry Communication Alcohol Dehydrogenase Acetophenones Stereoisomerism General Medicine General Chemistry Phenylethyl Alcohol Photochemical Processes Communications photobiocatalysis 3. Good health 0104 chemical sciences chemistry Photocatalysis Selectivity Oxidation-Reduction Acetophenone Visible spectrum |
| Zdroj: | Kroutil, W, Reischauer, S, Bierbaumer, S, Winkler, C K, Diaz-Rodriguez, A, J. Edwards, L, Kara, S, Mielke, T, Cartwright, J, Grogan, G, Pieber, B & Schmermund, L 2021, ' Chromoselective Photocatalysis Enables Stereocomplementary Biocatalytic Pathways ', Angewandte Chemie, vol. 60, no. 13, pp. 6965-6969 . https://doi.org/10.1002/anie.202100164 Angewandte Chemie International Edition Angewandte Chemie ChemRxiv Angewandte Chemie (International Ed. in English) Schmermund, L, Reischauer, S, Bierbaumer, S, Winkler, C K, Diaz-Rodriguez, A, Edwards, L J, Kara, S, Mielke, T, Cartwright, J, Grogan, G, Pieber, B & Kroutil, W 2021, ' Chromoselective Photocatalysis Enables Stereocomplementary Biocatalytic Pathways** ', Angewandte Chemie-International Edition, vol. 60, no. 13, pp. 6965-6969 . https://doi.org/10.1002/anie.202100164 |
| ISSN: | 1433-7851 |
| Popis: | 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. |
| Databáze: | OpenAIRE |
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