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<p>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 <i>E/Z</i> 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.</p>

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

  • 期刊论文

  • 出版模式：

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  • 发表日期：

    2025年11月26日

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  • Hang Luo,
  • Yupeng Yang,
  • Yunpeng Ma,
  • Fangnian Yu,
  • Min Gao,
  • Shizhao Xu,
  • Huawei Ju,
  • Yang Li,
  • Kaifeng Wu,
  • Luqing Lin

摘要

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.