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In situ copper photocatalysts triggering halide atom transfer of unactivated alkyl halides for general C(sp3)-N couplings

Author

Listed:
  • Hang Luo

    (Dalian University of Technology)

  • Yupeng Yang

    (Chinese Academy of Sciences Dalian)

  • Yukang Fu

    (Dalian University of Technology)

  • Fangnian Yu

    (Dalian University of Technology)

  • Lei Gao

    (Dalian University of Technology)

  • Yunpeng Ma

    (Dalian University of Technology)

  • Yang Li

    (Dalian University of Technology)

  • Kaifeng Wu

    (Chinese Academy of Sciences Dalian)

  • Luqing Lin

    (Dalian University of Technology)

Abstract

Direct reduction of unactivated alkyl halides for C(sp3)-N couplings under mild conditions presents a significant challenge in organic synthesis due to their low reduction potential. Herein, we introduce an in situ formed pyridyl-carbene-ligated copper (I) catalyst that is capable of abstracting halide atom and generating alkyl radicals for general C(sp3)-N couplings under visible light. Control experiments confirmed that the mono-pyridyl-carbene-ligated copper complex is the active species responsible for catalysis. Mechanistic investigations using transient absorption spectroscopy across multiple decades of timescales revealed ultrafast intersystem crossing (260 ps) of the photoexcited copper (I) complexes into their long-lived triplet excited states (>2 μs). The non-Stern-Volmer quenching dynamics of the triplets by unactivated alkyl halides suggests an association between copper (I) complexes and alkyl halides, thereby facilitating the abstraction of halide atoms via inner-sphere single electron transfer (SET), rather than outer-sphere SET, for the formation of alkyl radicals for subsequent cross couplings.

Suggested Citation

  • Hang Luo & Yupeng Yang & Yukang Fu & Fangnian Yu & Lei Gao & Yunpeng Ma & Yang Li & Kaifeng Wu & Luqing Lin, 2024. "In situ copper photocatalysts triggering halide atom transfer of unactivated alkyl halides for general C(sp3)-N couplings," Nature Communications, Nature, vol. 15(1), pages 1-11, December.
    • Handle: RePEc:nat:natcom:v:15:y:2024:i:1:d:10.1038_s41467-024-50082-w
    DOI: 10.1038/s41467-024-50082-w
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