Exploiting known enzymes for non-natural transformations that are inaccessible to chemocatalysts is highly desirable but challenging. In this presentation, I will discuss our recent studies on the discovery and engineering of new-to-nature reactivities in known enzymes by combining photocatalysis with enzymatic catalysis. In one example, we repurposed the ene-reductases (EREDs) to catalyze unprecedent enantioselective intermolecular radical hydroalkylation. This reaction reveals the promiscuous EREDs can achieve a reactivity that is difficult to realize by chemocatalysis, which will be useful for upgrading ‘ene’-containing compounds into value-added chemicals. In another example, we discovered that light irradiation could steer nicotinamide-dependent ketoreductases (KREDs) to catalyze an unnatural asymmetric radical transformation for the synthesis of valuable chiral compounds, which also shows potential for the upgrading of biomass-derived fatty acids. Additionally, capitalizing on the advantages of both photocatalysis and biocatalysis, we created a new chemoenzymatic route for the low-cost and expedient synthesis of various bridged bicyclic nitrogen heterocycles using EREDs and cheap starting materials. Overall, our studies have demonstrated that we could harness the astonishing new chemistry encoded in the known enzymes for novel chemical transformations.

Discovery and engineering of new-to-nature reactivities in known enzymes for novel chemical transformations

Fall 2022 abstracts, posters, and presentations will launch in mid-September.

ACS Fall 2022

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.