Asymmetric α‑Photoalkylation of β‑Ketocarbonyls by Primary Amine Catalysis: Facile Access to Acyclic All-Carbon Quaternary Stereocenters

We describe the direct construction of all-carbon quaternary stereocenters via α-photoalkylation of β-ketocarbonyls with high efficacy and enantioselectivities by merging photoredox catalysis and primary amine catalysis. The open-shell photoradical approach enables asymmetric α-alkylations that are difficult under thermal conditions.