Enzyme-controlled stereoselective radical cyclization to arenes enabled by metalloredox biocatalysis.

ABSTRACT: The effective induction of high levels of stereocontrol for free radical-mediated transformations represents a notorious challenge in asymmetric catalysis. Herein, we describe a novel metalloredox biocatalysis strategy to repurpose natural cytochromes P450 to catalyse asymmetric radical cyclisation to arenes through an unnatural electron transfer mechanism. Empowered by directed evolution, engineered P450s allowed diverse radical cyclisation selectivities to be accomplished in a catalyst-controlled fashion: P450_arc1 and P450_arc2 facilitated enantioconvergent transformations of racemic substrates, giving rise to either enantiomer of the product with excellent total turnover numbers (up to 12,000). In addition to these enantioconvergent variants, another engineered radi

SUBMITTER: Fu W 

PROVIDER: S-EPMC10882986 | biostudies-literature | 2023 Jul

REPOSITORIES: biostudies-literature