Light-driven radical copper-catalyzed allylic amination via allylic copper intermediates

作者：Hang Luo, Yupeng Yang, Yunpeng Ma, Fangnian Yu, Min Gao, Shutao Xu, Hui-Lin Ju, Yang Li, Kaifeng Wu, Luqing Lin · 发表于：Nature Communications · 年份：2025 · DOI：10.1038/s41467-025-64951-5 · 被引用次数：4 · 研究领域：Radical Photochemical Reactions、Catalytic C–H Functionalization Methods、Organoboron and organosilicon chemistry

The synthesis of allylic amines through an outer-sphere nucleophilic substitution mechanism involving electrophilic allyl copper(III) complexes with soft amines represents an uncharted territory in catalysis. This study introduces a radical-based approach for the generation of allylic copper(III) complexes, enabling the efficient synthesis of allylic amines in the presence of alkyl/aryl amines. Through copper photocatalysis, we demonstrate a radical-induced small-ring opening process that produces allylic amines featuring skipped double bonds, while simultaneously achieving highly regioselective 1,4-carboamination of 1,3-dienes with high E/Z selectivity. Mechanism studies substantiate the radical-mediated formation of allylic copper complexes and provide evidence for the involvement of outer-sphere nucleophilic substitution at allylic copper(III) complexes.