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oai:figshare.com:article/34041701 2026-10-01T09:04:56Z category_1 category_4 category_8 category_19 category_21 category_272 category_873 category_46 category_61 portal_63 item_type_6 month_year_10_2026

Enantioconvergent Deoxygenative Amination via Xanthate Esters by a Decarboxylative Relay Jing Wan (17137) Jacob A. Sanchez (24283040) Taotao Lu (2834198) Ramon Trevino (13007866) Zhanpeng Xue (25155551) Junkai Wan (5078291) Babu Raj Dhungana (20940598) Yao Sun (145327) Chao Huang (109404) Bethanie M. Avila (25155554) Min He (44052) Kai L. Shoemaker (25155557) Toby T. Skaria (24493167) Ramy Elerian (24283043) Maosheng Cheng (1409932) Oleg V. Larionov (1348758) Shengfei Jin (1409938) Biophysics Biochemistry Microbiology Pharmacology Biotechnology Environmental Sciences not elsewhere classified Chemical Sciences not elsewhere classified Immunology Developmental Biology mechanistically distinct platform mechanistic studies revealed derived xanthates via radical gating manifold mediates radical generation enantioselective radical gating deoxygenative radical pathways chiral benzylic amines benzylic radical radical activation chiral cobalt versatile strategy report herein producing α mild conditions high enantioselectivity findings establish direct conversion decarboxylative relay constructing c computational investigations c – broader potential bond homolysis acridine photocatalysis abundant precursors 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. 2026-10-01T00:00:00Z Text Journal contribution 10.1021/jacs.6c15980.s001 https://figshare.com/articles/journal_contribution/Enantioconvergent_Deoxygenative_Amination_via_Xanthate_Esters_by_a_Decarboxylative_Relay/34041701 CC BY-NC 4.0