Print Email Facebook Twitter Combining Photo-Organo Redox- and Enzyme Catalysis Facilitates Asymmetric C-H Bond Functionalization Title Combining Photo-Organo Redox- and Enzyme Catalysis Facilitates Asymmetric C-H Bond Functionalization Author Zhang, W. (TU Delft BT/Biocatalysis) Fernandez Fueyo, E. (TU Delft BN/Greg Bokinsky Lab) Hollmann, F. (TU Delft BT/Biocatalysis) Leemans Martin, L. (TU Delft BT/Biocatalysis) Pesic, M. (TU Delft BT/Biocatalysis) Wardenga, Rainer (Enzymicals AG, Greifswald) Höhne, Matthias (Greifswald University) Schmidt, S. (Graz University of Technology) Date 2018 Abstract In this study, we combined photo-organo redox catalysis and biocatalysis to achieve asymmetric C–H bond functionalization of simple alkane starting materials. The photo-organo catalyst anthraquinone sulfate (SAS) was employed to oxyfunctionalise alkanes to aldehydes and ketones. We coupled this light-driven reaction with asymmetric enzymatic functionalisations to yield chiral hydroxynitriles, amines, acyloins and α-chiral ketones with up to 99 % ee. In addition, we demonstrate functional group interconversion to alcohols, esters and carboxylic acids. The transformations can be performed as concurrent tandem reactions. We identified the degradation of substrates and inhibition of the biocatalysts as limiting factors affecting compatibility, due to reactive oxygen species generated in the photocatalytic step. These incompatibilities were addressed by reaction engineering, such as applying a two-phase system or temporal and spatial separation of the catalysts. Using a selection of eleven starting alkanes, one photo-organo catalyst and 8 diverse biocatalysts, we synthesized 26 products and report for the model compounds benzoin and mandelonitrile > 97 % ee at gram scale. Subject Asymmetric synthesisChemoenzymatic cascadesEnzymesPhoto-organo catalystPhotocatalysis To reference this document use: http://resolver.tudelft.nl/uuid:6fe70324-40e5-4ef4-a15f-0c02a5eab293 DOI https://doi.org/10.1002/ejoc.201801692 ISSN 1434-193X Source European Journal of Organic Chemistry Part of collection Institutional Repository Document type journal article Rights © 2018 W. Zhang, E. Fernandez Fueyo, F. Hollmann, L. Leemans Martin, M. Pesic, Rainer Wardenga, Matthias Höhne, S. Schmidt Files PDF Zhang_et_al_2018_European ... mistry.pdf 1.45 MB Close viewer /islandora/object/uuid:6fe70324-40e5-4ef4-a15f-0c02a5eab293/datastream/OBJ/view