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1,3-Difunctionalization of [1.1.1]propellane through iron-hydride catalyzed hydropyridylation

Author

Listed:
  • Changha Kim

    (Korea Advanced Institute of Science and Technology (KAIST)
    Institute for Basic Science (IBS))

  • Yuhyun Kim

    (Korea Advanced Institute of Science and Technology (KAIST)
    Institute for Basic Science (IBS))

  • Sungwoo Hong

    (Korea Advanced Institute of Science and Technology (KAIST)
    Institute for Basic Science (IBS))

Abstract

Current methodologies for the functionalization of [1.1.1]propellane primarily focus on achieving 1, 3-difunctionalized bicyclo[1.1.1]pentane or ring-opened cyclobutane moiety. Herein, we report an innovative approach for the 1, 3-difunctionalization of [1.1.1]propellane, enabling access to a diverse range of highly functionalized cyclobutanes via nucleophilic attack followed by ring opening and iron-hydride hydrogen atom transfer. To enable this method, we developed an efficient iron-catalyzed hydropyridylation of various alkenes for C − H alkylation of pyridines at the C4 position, eliminating the need for stoichiometric quantities of oxidants or reductants. Mechanistic investigations reveal that the resulting N-centered radical serves as an effective oxidizing agent, facilitating single-electron transfer oxidation of the reduced iron catalyst. This process efficiently sustains the catalytic cycle, offering significant advantages for substrates with oxidatively sensitive functionalities that are generally incompatible with alternative approaches. The strategy presented herein is not only mechanistically compelling but also demonstrates broad versatility, highlighting its potential for late-stage functionalization.

Suggested Citation

  • Changha Kim & Yuhyun Kim & Sungwoo Hong, 2024. "1,3-Difunctionalization of [1.1.1]propellane through iron-hydride catalyzed hydropyridylation," Nature Communications, Nature, vol. 15(1), pages 1-10, December.
  • Handle: RePEc:nat:natcom:v:15:y:2024:i:1:d:10.1038_s41467-024-50356-3
    DOI: 10.1038/s41467-024-50356-3
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    References listed on IDEAS

    as
    1. Hangyeol Choi & Gangadhar Rao Mathi & Seonghyeok Hong & Sungwoo Hong, 2022. "Enantioselective functionalization at the C4 position of pyridinium salts through NHC catalysis," Nature Communications, Nature, vol. 13(1), pages 1-8, December.
    2. Jianming Yan & Haidi Tang & Eugene Jun Rong Kuek & Xiangcheng Shi & Chenguang Liu & Muliang Zhang & Jared L. Piper & Shengquan Duan & Jie Wu, 2021. "Divergent functionalization of aldehydes photocatalyzed by neutral eosin Y with sulfone reagents," Nature Communications, Nature, vol. 12(1), pages 1-10, December.
    3. Xiaheng Zhang & Russell T. Smith & Chip Le & Stefan J. McCarver & Brock T. Shireman & Nicholas I. Carruthers & David W. C. MacMillan, 2020. "Copper-mediated synthesis of drug-like bicyclopentanes," Nature, Nature, vol. 580(7802), pages 220-226, April.
    4. Isabelle Nathalie-Marie Leibler & Makeda A. Tekle-Smith & Abigail G. Doyle, 2021. "A general strategy for C(sp3)–H functionalization with nucleophiles using methyl radical as a hydrogen atom abstractor," Nature Communications, Nature, vol. 12(1), pages 1-10, December.
    5. Yonghoon Moon & Bohyun Park & Inwon Kim & Gyumin Kang & Sanghoon Shin & Dahye Kang & Mu-Hyun Baik & Sungwoo Hong, 2019. "Visible light induced alkene aminopyridylation using N-aminopyridinium salts as bifunctional reagents," Nature Communications, Nature, vol. 10(1), pages 1-9, December.
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