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Practical and regioselective halonitrooxylation of olefins to access β-halonitrates

Author

Listed:
  • Xuan Cheng

    (Shanghai Normal University
    Shanghai Normal University)

  • Quan Yin

    (Shanghai Normal University
    Shanghai Normal University)

  • Yi-Fei Cheng

    (Shanghai Normal University
    Shanghai Normal University)

  • Shao-Hua Wu

    (Shanghai Normal University
    Shanghai Normal University)

  • Xin-Chang Sun

    (Shanghai Normal University
    Shanghai Normal University)

  • De-Yi Kong

    (Shanghai Normal University
    Shanghai Normal University)

  • Qing-Hai Deng

    (Shanghai Normal University
    Shanghai Normal University)

Abstract

Organic nitrates, as effective donors of the signaling molecule nitric oxide, are widely applied in the pharmaceutical industry. However, practical and efficient methods for accessing organic nitrates are still scarce, and achieving high regiocontrol in unactivated alkene difunctionalization remains challenging. Here we present a simple and practical method for highly regioselective halonitrooxylation of unactivated alkenes. The approach utilizes TMSX (X: Cl, Br, or I) and oxybis(aryl-λ3-iodanediyl) dinitrates (OAIDN) as sources of halogen and nitrooxy groups, with 0.5 mol % FeCl3 as the catalyst. Remarkably, high regioselectivity in the halonitrooxylation of aromatic alkenes can be achieved even without any catalyst. This protocol features easy scalability and excellent functional group compatibility, providing a range of β-halonitrates (127 examples, up to 99% yield, up to >20:1 rr). Notably, 2-iodoethyl nitrate, a potent synthon derived from ethylene, reacts smoothly with a variety of functional units to incorporate the nitrooxy group into the desired molecules.

Suggested Citation

  • Xuan Cheng & Quan Yin & Yi-Fei Cheng & Shao-Hua Wu & Xin-Chang Sun & De-Yi Kong & Qing-Hai Deng, 2024. "Practical and regioselective halonitrooxylation of olefins to access β-halonitrates," Nature Communications, Nature, vol. 15(1), pages 1-10, December.
    • Handle: RePEc:nat:natcom:v:15:y:2024:i:1:d:10.1038_s41467-024-51655-5
    DOI: 10.1038/s41467-024-51655-5
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    References listed on IDEAS

    as
    1. Xianxiao Chen & Weidong Rao & Tao Yang & Ming Joo Koh, 2020. "Alkyl halides as both hydride and alkyl sources in catalytic regioselective reductive olefin hydroalkylation," Nature Communications, Nature, vol. 11(1), pages 1-9, December.
    2. Xiao-Si Hu & Jun-Xiong He & Su-Zhen Dong & Qiu-Hua Zhao & Jin-Sheng Yu & Jian Zhou, 2020. "Regioselective Markovnikov hydrodifluoroalkylation of alkenes using difluoroenoxysilanes," Nature Communications, Nature, vol. 11(1), pages 1-9, December.
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