Detailed herein is the photochemical organocatalytic enantioselective α-alkylation of aldehydes with (phenylsulfonyl)alkyl iodides. The chemistry relies on the direct photoexcitation of enamines to trigger the formation of reactive carbon-centered radicals from iodosulfones, while the ground-state chiral enamines provide effective stereochemical control over the radical trapping process. The ph...