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Electro-oxidative amination of benzylic C(sp³)–C(sp³) bonds in aromatic hydrocarbons

Author

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  • Kai-Xuan Yang

    (Shanghai Jiao Tong University)

  • Shu-Fan He

    (Shanghai Jiao Tong University)

  • Qinhui Wan

    (Shanghai Jiao Tong University)

  • Tianyi Xu

    (Shanghai Jiao Tong University)

  • Daixi Li

    (Xiamen University
    Fujian Medical University)

  • Kexin Liu

    (Zhongyuan University of Technology)

  • Wenying Ai

    (Zhongyuan University of Technology)

  • Tao Shen

    (Shanghai Jiao Tong University)

Abstract

C(sp3)-C(sp3) amination represents a promising approach for synthesizing various amines, facilitating applications from late-stage scaffold hopping to the degradation of polymers and biomass. However, it remains challenging due to the inertness of the C-C bond and difficulties in controlling regio- and chemo-selectivity. Herein, we report an electro-oxidative benzylic C(sp3)-C(sp3) amination reaction of aromatic hydrocarbons using nitriles, amides, and sulfonamides as nucleophiles. This process occurs under mild conditions with hydrogen evolution, eliminating the need for external oxidants or transition metal catalysts. Mechanism involves successive anodic oxidative cleavage of the benzylic C(sp3)-C(sp3) bond to generate two carbocation fragments, which are subsequently captured by nucleophiles to form two C-N bonds. Mechanistic studies suggest that HFIP is critical as additive in adjusting the oxidation potentials of alkylbenzene substrates and amine products, effectively preventing overoxidation of products.

Suggested Citation

  • Kai-Xuan Yang & Shu-Fan He & Qinhui Wan & Tianyi Xu & Daixi Li & Kexin Liu & Wenying Ai & Tao Shen, 2025. "Electro-oxidative amination of benzylic C(sp³)–C(sp³) bonds in aromatic hydrocarbons," Nature Communications, Nature, vol. 16(1), pages 1-9, December.
    • Handle: RePEc:nat:natcom:v:16:y:2025:i:1:d:10.1038_s41467-025-61017-4
    DOI: 10.1038/s41467-025-61017-4
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    References listed on IDEAS

    as
    1. Liang Ge & Chi Zhang & Chengkai Pan & Ding-Xing Wang & Dong-Ying Liu & Zhi-Qiang Li & Pingkang Shen & Lifang Tian & Chao Feng, 2022. "Photoredox-catalyzed C–C bond cleavage of cyclopropanes for the formation of C(sp3)–heteroatom bonds," Nature Communications, Nature, vol. 13(1), pages 1-13, December.
    2. Nils Frank & Jeremy Nugent & Bethany R. Shire & Helena D. Pickford & Patrick Rabe & Alistair J. Sterling & Tryfon Zarganes-Tzitzikas & Thomas Grimes & Amber L. Thompson & Russell C. Smith & Christophe, 2022. "Synthesis of meta-substituted arene bioisosteres from [3.1.1]propellane," Nature, Nature, vol. 611(7937), pages 721-726, November.
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