Multicomponent Construction\nof Tertiary Alkylamines\nby Photoredox/Nickel-Catalyzed Aminoalkylation of Organohalides

Tertiary alkylamines are privileged structural motifs\nwidely present\nin natural products, pharmaceutical agents, and bioactive molecules,\nand their efficient synthesis has been a longstanding goal in organic\nchemistry. The functionalization of α-amino radicals derived\nfrom abundant precursors represents an emerging approach to accessing\nalkylamines, but application of this strategy to obtain tertiary alkylamines\nremains challenging. Here, we show that dual photoredox/nickel catalysis\nenables aminoalkylation of organohalides (sp<sup>2</sup>- and sp<sup>3</sup>-hybridized) in combination with secondary alkylamines and\naldehydes. The multicomponent process proceeds through selective generation\nof α-amino radicals from the reduction of in situ-generated\niminium ions by photoredox catalysis, followed by nickel-catalyzed\ncross-coupling to build a wide array of functionally diverse tertiary\nalkylamines. This strategy could also be extended to unprecedented\nfour-component reactions and their asymmetric variants to deliver\nenantioenriched α-aryl-substituted γ-amino acid derivatives.\nTaken together, this work offers a streamlined synthetic route to\naliphatic tertiary amines.