Enantioselective Chemodivergent Three-Component Radical Tandem Reactions through Asymmetric Photoredox Catalysis

Chemodivergent synthesis has been achieved in asymmetric photocatalysis. Under a dual catalyst system consisting of a chiral phosphoric acid and DPZ as a photosensitizer, different inorganic bases enabled the formation of two sets of valuable products from the three-component radical tandem transformations of 2-bromo-1-arylenthan-1-ones, styrenes, and quinoxalin2(1H)-ones. The key to success was the distinct pK(a) environment, in which the radicals that formed on the quinoxalin-2(1H)-one rings after two radical addition processes underwent either single-electron oxidation or single-electron reduction. In addition, this work represents the first use of quinoxalin-2(1H)-ones in asymmetric photoredox catalysis.

Automated summary

Chemodivergent synthesis was achieved using asymmetric photocatalysis. By using a dual catalyst system consisting of a chiral phosphoric acid and DPZ as a photosensitizer, different inorganic bases were used to enable the formation of two sets of valuable products from a three-component radical tandem transformation. The key to success was the distinct pK(a) environment, which determined the fate of the radicals formed on the quinoxalin-2(1H)-one rings.