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Highly selective single and multiple deuteration of unactivated C(sp3)-H bonds

Author

Listed:
  • Nian Li

    (Nanjing University)

  • Jinhang Li

    (Nanjing University)

  • Mingzhe Qin

    (Nanjing University)

  • Jiajun Li

    (Nanjing University)

  • Jie Han

    (Nanjing University)

  • Chengjian Zhu

    (Nanjing University
    Shanghai Institute of Organic Chemistry
    Zhengzhou University)

  • Weipeng Li

    (Nanjing University)

  • Jin Xie

    (Nanjing University
    Xinjiang University)

Abstract

Selective deuteration of unactivated C(sp3)-H bonds is a highly attractive but challenging subject of research in pharmaceutical chemistry, material science and synthetic chemistry. Reported herein is a practical, highly selective and economical efficient hydrogen/deuterium (H/D) exchange of unactivated C(sp3)-H bonds by synergistic photocatalysis and hydrogen atom transfer (HAT) catalysis. With the easily prepared PMP-substituted amides as nitrogen-centered radical precursors, a wide range of structurally diverse amides can undergo predictable radical H/D exchange smoothly with inexpensive D2O as the sole deuterium source, giving rise to the distal tertiary, secondary and primary C(sp3)-H bonds selectively deuterated products in yields of up to 99% and excellent D-incorporations. In addition to precise monodeuteration, this strategy can also achieve multideuteration of the substrates contain more than one remote C(sp3)-H bond, which opens a method to address multi-functionalization of distal unactivated C(sp3)–H bonds.

Suggested Citation

  • Nian Li & Jinhang Li & Mingzhe Qin & Jiajun Li & Jie Han & Chengjian Zhu & Weipeng Li & Jin Xie, 2022. "Highly selective single and multiple deuteration of unactivated C(sp3)-H bonds," Nature Communications, Nature, vol. 13(1), pages 1-8, December.
    • Handle: RePEc:nat:natcom:v:13:y:2022:i:1:d:10.1038_s41467-022-31956-3
    DOI: 10.1038/s41467-022-31956-3
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    References listed on IDEAS

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    1. John C. K. Chu & Tomislav Rovis, 2016. "Amide-directed photoredox-catalysed C–C bond formation at unactivated sp3 C–H bonds," Nature, Nature, vol. 539(7628), pages 272-275, November.
    2. Gilbert J. Choi & Qilei Zhu & David C. Miller & Carol J. Gu & Robert R. Knowles, 2016. "Catalytic alkylation of remote C–H bonds enabled by proton-coupled electron transfer," Nature, Nature, vol. 539(7628), pages 268-271, November.
    3. Jacob A. Smith & Katy B. Wilson & Reilly E. Sonstrom & Patrick J. Kelleher & Kevin D. Welch & Emmit K. Pert & Karl S. Westendorff & Diane A. Dickie & Xiaoping Wang & Brooks H. Pate & W. Dean Harman, 2020. "Preparation of cyclohexene isotopologues and stereoisotopomers from benzene," Nature, Nature, vol. 581(7808), pages 288-293, May.
    4. Muliang Zhang & Jin Xie & Chengjian Zhu, 2018. "A general deoxygenation approach for synthesis of ketones from aromatic carboxylic acids and alkenes," Nature Communications, Nature, vol. 9(1), pages 1-10, December.
    5. Yantao Li & Qianzhen Shao & Hengchi He & Chengjian Zhu & Xiao-Song Xue & Jin Xie, 2022. "Highly selective synthesis of all-carbon tetrasubstituted alkenes by deoxygenative alkenylation of carboxylic acids," Nature Communications, Nature, vol. 13(1), pages 1-8, December.
    6. Rehanguli Ruzi & Kai Liu & Chengjian Zhu & Jin Xie, 2020. "Upgrading ketone synthesis direct from carboxylic acids and organohalides," Nature Communications, Nature, vol. 11(1), pages 1-9, December.
    7. Yanjun Li & Ziqi Ye & Yu-Mei Lin & Yan Liu & Yumeng Zhang & Lei Gong, 2021. "Organophotocatalytic selective deuterodehalogenation of aryl or alkyl chlorides," Nature Communications, Nature, vol. 12(1), pages 1-13, December.
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    Cited by:

    1. Chaodong Wang & Zhi Chen & Jie Sun & Luwei Tong & Wenjian Wang & Shengjie Song & Jianjun Li, 2024. "Sulfonamide-directed site-selective functionalization of unactivated C(sp3)−H enabled by photocatalytic sequential electron/proton transfer," Nature Communications, Nature, vol. 15(1), pages 1-11, December.

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