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.