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Regio-, stereo-, and enantioselective ipso- and migratory defluorinative olefin cross-coupling to access highly functionalized monofluoroalkenes

Author

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  • Daning Zeng

    (Nanjing University)

  • Zihao Liu

    (Nanjing University)

  • Guoce Huang

    (Nanjing University)

  • You Wang

    (Nanjing University)

  • Shaolin Zhu

    (Nanjing University
    Henan Normal University
    Shanghai Jiao Tong University)

Abstract

Monofluoroalkenes serve as nonhydrolyzable mimetics of amides and are frequently encountered in drug candidates. Herein we report a regio-, enantio-, and stereoselective NiH-catalyzed ipso- and migratory defluorinative olefin cross-coupling employing readily available olefins and gem-difluoroalkenes under mild conditions. This approach enables the efficient synthesis of a broad array of structurally diverse monofluoroalkenes bearing a tertiary allylic stereogenic center. Mechanistically, the challenging migratory defluorinative olefin cross-coupling process is successfully realized through a ligand relay catalytic strategy, enabling the formal C(sp3)–H/C(sp2)–F activation with high levels of regio-, stereo-, and enantiocontrol.

Suggested Citation

  • Daning Zeng & Zihao Liu & Guoce Huang & You Wang & Shaolin Zhu, 2024. "Regio-, stereo-, and enantioselective ipso- and migratory defluorinative olefin cross-coupling to access highly functionalized monofluoroalkenes," Nature Communications, Nature, vol. 15(1), pages 1-9, December.
  • Handle: RePEc:nat:natcom:v:15:y:2024:i:1:d:10.1038_s41467-024-52054-6
    DOI: 10.1038/s41467-024-52054-6
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    References listed on IDEAS

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    1. Francisco Juliá-Hernández & Toni Moragas & Josep Cornella & Ruben Martin, 2017. "Remote carboxylation of halogenated aliphatic hydrocarbons with carbon dioxide," Nature, Nature, vol. 545(7652), pages 84-88, May.
    2. Panpan Tian & Chao Feng & Teck-Peng Loh, 2015. "Rhodium-catalysed C(sp2)–C(sp2) bond formation via C–H/C–F activation," Nature Communications, Nature, vol. 6(1), pages 1-7, November.
    3. Yulong Zhang & Xianfeng Xu & Shaolin Zhu, 2019. "Nickel-catalysed selective migratory hydrothiolation of alkenes and alkynes with thiols," Nature Communications, Nature, vol. 10(1), pages 1-9, December.
    4. Yufeng Sun & Jun Guo & Xuzhong Shen & Zhan Lu, 2022. "Ligand relay catalysis for cobalt-catalyzed sequential hydrosilylation and hydrohydrazidation of terminal alkynes," Nature Communications, Nature, vol. 13(1), pages 1-9, December.
    5. Caiyou Chen & Jonas C. Peters & Gregory C. Fu, 2021. "Photoinduced copper-catalysed asymmetric amidation via ligand cooperativity," Nature, Nature, vol. 596(7871), pages 250-256, August.
    6. Zhaobin Wang & Haolin Yin & Gregory C. Fu, 2018. "Catalytic enantioconvergent coupling of secondary and tertiary electrophiles with olefins," Nature, Nature, vol. 563(7731), pages 379-383, November.
    7. Yuli He & Jiawei Ma & Huayue Song & Yao Zhang & Yong Liang & You Wang & Shaolin Zhu, 2022. "Regio- and enantioselective remote hydroarylation using a ligand-relay strategy," Nature Communications, Nature, vol. 13(1), pages 1-9, December.
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