IDEAS home Printed from https://ideas.repec.org/a/nat/natcom/v15y2024i1d10.1038_s41467-024-50356-3.html
   My bibliography  Save this article

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
    as

    Download full text from publisher

    File URL: https://www.nature.com/articles/s41467-024-50356-3
    File Function: Abstract
    Download Restriction: no

    File URL: https://libkey.io/10.1038/s41467-024-50356-3?utm_source=ideas
    LibKey link: if access is restricted and if your library uses this service, LibKey will redirect you to where you can use your library subscription to access this item
    ---><---

    References listed on IDEAS

    as
    1. 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.
    2. 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.
    3. 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.
    4. 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.
    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.
    Full references (including those not matched with items on IDEAS)

    Most related items

    These are the items that most often cite the same works as this one and are cited by the same works as this one.
    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. Yujun Li & Shaopeng Guo & Qing-Han Li & Ke Zheng, 2023. "Metal-free photoinduced C(sp3)–H/C(sp3)–H cross-coupling to access α‑tertiary amino acid derivatives," Nature Communications, Nature, vol. 14(1), pages 1-9, December.
    3. 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.
    4. Heather A. Hintz & Christo S. Sevov, 2022. "Catalyst-controlled functionalization of carboxylic acids by electrooxidation of self-assembled carboxyl monolayers," Nature Communications, Nature, vol. 13(1), pages 1-7, December.
    5. Xiaochen Wang & Rongxin Yang & Binbing Zhu & Yuxiu Liu & Hongjian Song & Jianyang Dong & Qingmin Wang, 2023. "Direct allylic acylation via cross-coupling involving cooperative N‑heterocyclic carbene, hydrogen atom transfer, and photoredox catalysis," Nature Communications, Nature, vol. 14(1), pages 1-10, December.
    6. Mingshuo Chen & Yuang Cui & Xiaoping Chen & Rui Shang & Xiaheng Zhang, 2024. "C−F bond activation enables synthesis of aryl difluoromethyl bicyclopentanes as benzophenone-type bioisosteres," Nature Communications, Nature, vol. 15(1), pages 1-10, December.
    7. Mingrui Li & Yingtao Wu & Xiao Song & Jiaqiong Sun & Zuxiao Zhang & Guangfan Zheng & Qian Zhang, 2024. "Visible light-mediated organocatalyzed 1,3-aminoacylation of cyclopropane employing N-benzoyl saccharin as bifunctional reagent," Nature Communications, Nature, vol. 15(1), pages 1-9, December.

    More about this item

    Statistics

    Access and download statistics

    Corrections

    All material on this site has been provided by the respective publishers and authors. You can help correct errors and omissions. When requesting a correction, please mention this item's handle: RePEc:nat:natcom:v:15:y:2024:i:1:d:10.1038_s41467-024-50356-3. See general information about how to correct material in RePEc.

    If you have authored this item and are not yet registered with RePEc, we encourage you to do it here. This allows to link your profile to this item. It also allows you to accept potential citations to this item that we are uncertain about.

    If CitEc recognized a bibliographic reference but did not link an item in RePEc to it, you can help with this form .

    If you know of missing items citing this one, you can help us creating those links by adding the relevant references in the same way as above, for each refering item. If you are a registered author of this item, you may also want to check the "citations" tab in your RePEc Author Service profile, as there may be some citations waiting for confirmation.

    For technical questions regarding this item, or to correct its authors, title, abstract, bibliographic or download information, contact: Sonal Shukla or Springer Nature Abstracting and Indexing (email available below). General contact details of provider: http://www.nature.com .

    Please note that corrections may take a couple of weeks to filter through the various RePEc services.

    IDEAS is a RePEc service. RePEc uses bibliographic data supplied by the respective publishers.