biostudies-literatureKong MNSFCNational Natural Science Foundation of ChinaHenan Key Laboratory of Organic Functional Molecules and Drug Innovatione2307773https://www.ebi.ac.uk/biostudies/studies/S-EPMC10966550biostudies-literatureUnknown11(12)An unprecedented enantioselective protonation reaction enabled by photoredox catalytic radical coupling is developed. Under cooperative dicynopyrazine-derived chromophore (DPZ) as a photosensitizer and a chiral phosphoric acid catalyst, and Hantzsch ester as a sacrificial reductant, the transformations between α-substituted enones and cyanoazaarenes or 2-(chloromethyl)azaaren-1-iums can proceed a tandem reduction, radical coupling, and enantioselective protonation process efficiently. Two classes of pharmaceutically important enantioenriched azaarene variants, which contain a synthetically versatile ketone-substituted tertiary carbon stereocenter at the β- or γ-position of the azaarenes, are synthesized with high yields and ees.Advanced science (Weinheim, Baden-Wurttemberg, Germany)Radical Cross Coupling and Enantioselective Protonation through Asymmetric Photoredox Catalysis.PMC109665502217107221925103Yin YKong MJiang ZZhang JBan XWang ZZhao XfalseRadical Cross Coupling and Enantioselective Protonation through Asymmetric Photoredox Catalysis.An unprecedented enantioselective protonation reaction enabled by photoredox catalytic radical coupling is developed. Under cooperative dicynopyrazine-derived chromophore (DPZ) as a photosensitizer and a chiral phosphoric acid catalyst, and Hantzsch ester as a sacrificial reductant, the transformations between α-substituted enones and cyanoazaarenes or 2-(chloromethyl)azaaren-1-iums can proceed a tandem reduction, radical coupling, and enantioselective protonation process efficiently. Two classes of pharmaceutically important enantioenriched azaarene variants, which contain a synthetically versatile ketone-substituted tertiary carbon stereocenter at the β- or γ-position of the azaarenes, are synthesized with high yields and ees.2024-01-01T00:00:00Z2024 Mar2025-04-25T21:41:49.821Z2025-04-06T08:48:46.696ZS-EPMC109665503823315210.1002/advs.202307773