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

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.

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Publication Details

Journal
Nature Communications
Published
2025-11-26
DOI
https://doi.org/10.1038/s41467-025-64951-5
Citations
1
Primary Topic
Radical Photochemical Reactions
Type
article
Field-Weighted Citation Impact
0.94

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article

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

Luqing Lin, Yang Li, Fangnian Yu, Yunpeng Ma et al.
1 citations
Nature Communications
Radical Photochemical Reactions
0.94
article

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

Luqing Lin, Yang Li, Fangnian Yu, Yunpeng Ma, Kaifeng Wu, Min Gao, Hui-Lin Ju, Shutao Xu, Yupeng Yang, Hang Luo
article en
1 citations

Abstract

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.

Nature CommunicationsVol. 16(1)
Hokkaido University of Science (JP), Dalian Institute of Chemical Physics (CN), Nankai University (CN), Hokkaido University (JP), Dalian University of Technology (CN), Dalian University (CN), Dalian Municipal Central Hospital (CN)
Ministry of Education, Culture, Sports, Science and Technology, National Natural Science Foundation of China, Chinese Academy of Sciences, Nankai University, Hokkaido University, Japan Society for the Promotion of Science
Openalex Percentile: Top 19%
Radical Photochemical Reactions
0.94
DOIOpen Access PDFOpenAlex
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