Detailed herein is the photochemical organocatalytic enantioselective a-alkylation of aldehydes with (phenylsulfo- nyl)alkyl iodides. The chemistry relies on the direct photo- excitation 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 phenylsulfonyl moiety, acting as a redox auxiliary group, facilitates the generation of radicals. In addition, it can eventually be removed under mild reducing conditions to reveal methyl and benzyl groups.