Photochemical organocatalytic enantioselective radical γ-functionalization of α-branched enals

Reported herein is a rare example of asymmetric catalytic functionalisation of enals at the remote γ-position, proceeding via a radical path. The process requires visible light and exploits the synergistic actions of two distinct organocatalysts. A nucleophilic organic catalyst generates radicals upon S_N2-based activation of commercially available alkyl halides and blue light irradiation. Concomitantly, a chiral secondary amine catalyst triggers the formation of a dienamine from α-branched enals. This chiral dienamine intercepts the photogenerated radicals with excellent γ-selectivity and good stereocontrol.