The Natural Redox Cofactor Pyrroloquinoline Quinone (PQQ) Enables Photocatalytic Radical Cyclizations.

ABSTRACT: Photoenzymatic catalysis facilitates stereoselective new-to-nature chemistry under mild conditions. In addition to the rational design of artificial photoenzymes, naturally occurring redox enzymes can be repurposed to promote photoredox catalysis in the chiral protein environment. Here, we show that enzymes utilizing the pyrroloquinoline quinone (PQQ) cofactor expand the toolbox of photobiocatalysis. PQQ absorbs visible light and is capable of single-electron transfer. It thus exhibits mechanistic similarities to flavin cofactors, which are widely used for photoenzymatic approaches. First, we established the trimethyl ester PQQMe₃ as a stand-alone photoredox catalyst in pure organic solvent. Upon excitation, PQQMe₃ enables the redox-neutral radical cyclization of an N

SUBMITTER: Bahukhandi SB 

PROVIDER: S-EPMC12462760 | biostudies-literature | 2025 Sep

REPOSITORIES: biostudies-literature