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Deoxygenative radical cross-coupling of C(sp3)−O/C(sp3)−H bonds promoted by hydrogen-bond interaction

Author

Listed:
  • Yue Wang

    (Southern Medical University
    Chinese Academy of Sciences)

  • Suping Zhang

    (Chinese Academy of Sciences
    Guangzhou University of Chinese Medicine)

  • Ke Zeng

    (Chinese Academy of Sciences)

  • Pengli Zhang

    (Chinese Academy of Sciences)

  • Xiaorong Song

    (Chinese Academy of Sciences)

  • Tie-Gen Chen

    (Southern Medical University
    Chinese Academy of Sciences)

  • Guoqin Xia

    (Southern Medical University
    Chinese Academy of Sciences)

Abstract

Building C(sp3)-rich architectures using simple and readily available starting materials will greatly advance modern drug discovery. C(sp3)−H and C(sp3)−O bonds are commonly used to strategically disassemble and construct bioactive compounds, respectively. However, the direct cross coupling of these two chemical bonds to form C(sp3)−C(sp3) bonds is rarely explored in existing literature. Conventional methods for forming C(sp3)−C(sp3) bonds via radical-radical coupling pathways often suffer from poor selectivity, severely limiting their practicality in synthetic applications. In this study, we present a single electron transfer (SET) strategy that enables the cleavage of amine α-C − H bonds and heterobenzylic C − O bonds to form C(sp3)−C(sp3) bonds. Preliminary mechanistic studies reveal a hydrogen bond interaction between substrates and phosphoric acid facilitates the cross-coupling of two radicals with high chemoselectivity. This methodology provides an effective approach to a variety of aza-heterocyclic unnatural amino acids and bioactive molecules.

Suggested Citation

  • Yue Wang & Suping Zhang & Ke Zeng & Pengli Zhang & Xiaorong Song & Tie-Gen Chen & Guoqin Xia, 2024. "Deoxygenative radical cross-coupling of C(sp3)−O/C(sp3)−H bonds promoted by hydrogen-bond interaction," Nature Communications, Nature, vol. 15(1), pages 1-8, December.
    • Handle: RePEc:nat:natcom:v:15:y:2024:i:1:d:10.1038_s41467-024-50897-7
    DOI: 10.1038/s41467-024-50897-7
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    References listed on IDEAS

    as
    1. Zhe Dong & David W. C. MacMillan, 2021. "Metallaphotoredox-enabled deoxygenative arylation of alcohols," Nature, Nature, vol. 598(7881), pages 451-456, October.
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    3. Ian B. Perry & Thomas F. Brewer & Patrick J. Sarver & Danielle M. Schultz & Daniel A. DiRocco & David W. C. MacMillan, 2018. "Direct arylation of strong aliphatic C–H bonds," Nature, Nature, vol. 560(7716), pages 70-75, August.
    4. 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.
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