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

Hang Luo, Yupeng Yang, Yukang Fu, Fangnian Yu, Lei Gao, Yunpeng Ma, Yang Li (), Kaifeng Wu () and Luqing Lin ()
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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

Nature Communications, 2024, vol. 15, issue 1, 1-11

Abstract: 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.

Date: 2024
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DOI: 10.1038/s41467-024-50082-w

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