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Visible-light-driven external-photocatalyst-free alkylative carboxylation of alkenes with CO2

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Abstract

Herein, we report a novel protocol for visible-light-driven alkylative carboxylation of alkenes with CO2 in the absence of external photocatalyst. Under the irradiation of visible light, a variety of 4-alkyl-1,4-dihydropyridines (alkyl-DHPs) serve as not only alkyl radical precursors but also photoexcited reductants probably with the potential to reduce benzyl radicals. Several styrenes and acrylates are applicable in this reaction to give structurally diverse carboxylic acids in good to excellent yields. These reactions feature mild reaction conditions (1 atm of CO2, room temperature, visible light, photocatalyst- and transition metal-free), good functional group tolerance, easy scalability, as well as high regio-, and chemo-selectivity. Mechanistic investigations provide evidence that alkyl radical, benzyl radical and carbanion might be involved in this reaction, providing a novel strategy for CO2 utilization.

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Acknowledgements

This work was supported by the National Natural Science Foundation of China (21822108, 21772129), the Fok Ying Tung Education Foundation (161013), Sichuan Science and Technology Program (20CXTD0112), and Fundamental Research Funds for the Central Universities.

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Author notes

  1. These authors contributed equally to this work.

Authors and Affiliations

  1. Urumqi Key Laboratory of Green Catalysis and Synthesis Technology; Key Laboratory of Energy Materials Chemistry, Ministry of Education; Key Laboratory of Advanced Functional Materials, Autonomous Region; College of Chemistry, Xinjiang University, Urumqi, 830046, China

    Ya-Nan Niu & Yu-Ming Yu

  2. Key Laboratory of Green Chemistry & Technology of Ministry of Education, College of Chemistry, Sichuan University, Chengdu, 610064, China

    Xing-Hao Jin, Li-Li Liao, He Huang, Bo Yu & Da-Gang Yu

Authors
  1. Ya-Nan Niu
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  2. Xing-Hao Jin
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  3. Li-Li Liao
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  4. He Huang
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  5. Bo Yu
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  6. Yu-Ming Yu
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  7. Da-Gang Yu
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Correspondence to Yu-Ming Yu or Da-Gang Yu.

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The authors declare no conflict of interest.

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Niu, YN., Jin, XH., Liao, LL. et al. Visible-light-driven external-photocatalyst-free alkylative carboxylation of alkenes with CO2. Sci. China Chem. 64, 1164–1169 (2021). https://doi.org/10.1007/s11426-021-1004-y

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  • DOI: https://doi.org/10.1007/s11426-021-1004-y

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