Combining Photo-Organo Redox- and Enzyme Catalysis Facilitates Asymmetric C-H Bond Functionalization

Wuyuan Zhang, Elena Fernandez Fueyo, Frank Hollmann, Laura Leemans Martin, Milja Pesic, Rainer Wardenga, Matthias Höhne, Sandy Schmidt

Research output: Contribution to journalArticleScientificpeer-review

16 Citations (Scopus)
31 Downloads (Pure)

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.

Original languageEnglish
Number of pages6
JournalEuropean Journal of Organic Chemistry
DOIs
Publication statusPublished - 2018

Keywords

  • Asymmetric synthesis
  • Chemoenzymatic cascades
  • Enzymes
  • Photo-organo catalyst
  • Photocatalysis

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