Enantioconvergent Deoxygenative Amination via Xanthate Esters by a Decarboxylative Relay

The direct conversion of alcohols to amines through deoxygenative radical pathways can provide a versatile strategy for constructing C(sp3)-N bonds from simple and abundant precursors, yet catalytic enantioconvergent variants remain undeveloped. We report herein a previously unexplored enantioconvergent deoxygenative amination that proceeds by radical activation of alcohol-derived xanthates via a decarboxylative radical relay process. This transformation is enabled by the merger of acridine photocatalysis, which mediates radical generation, and chiral cobalt(salen) catalysis, which mediates asymmetric radical-polar crossover, producing α-chiral benzylic amines under mild conditions. The method provides efficient access to medicinally relevant amine scaffolds with high enantioselectivity. Mechanistic studies revealed a radical gating manifold in which the cobalt catalyst selectively mediates the C-N coupling with the benzylic radical in preference to a competing decarboxylative amination pathway. Computational investigations further elucidated the structural and electronic factors governing xanthate activation, C-O bond homolysis, and the enantioselective radical gating by the cobalt catalyst. Together, these findings establish a mechanistically distinct platform for asymmetric deoxygenative C-N bond formation and highlight the broader potential of cobalt-catalyzed radical gating based on the radical-polar crossover in the development of enantioconvergent radical relay transformations.