IDEAS home Printed from https://ideas.repec.org/a/nat/natcom/v13y2022i1d10.1038_s41467-022-31956-3.html
   My bibliography  Save this article

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
    as

    Download full text from publisher

    File URL: https://www.nature.com/articles/s41467-022-31956-3
    File Function: Abstract
    Download Restriction: no
    File URL: https://libkey.io/10.1038/s41467-022-31956-3?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. 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.
    Full references (including those not matched with items on IDEAS)

    Citations

    Citations are extracted by the CitEc Project, subscribe to its RSS feed for this item.
    as


    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.
    2. Kai Sun & Chang Ge & Xiaolan Chen & Bin Yu & Lingbo Qu & Bing Yu, 2024. "Energy-transfer-enabled photocatalytic transformations of aryl thianthrenium salts," Nature Communications, Nature, vol. 15(1), pages 1-9, December.
    3. Yuanli Xu & Wenlong Chen & Ruihua Pu & Jia Ding & Qing An & Yi Yang & Weimin Liu & Zhiwei Zuo, 2024. "Selective monodeuteration enabled by bisphosphonium catalyzed ring opening processes," Nature Communications, Nature, vol. 15(1), pages 1-9, December.

    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. 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.
    2. Shuaishuai Wang & Tingrui Li & Chengyihan Gu & Jie Han & Chuan-Gang Zhao & Chengjian Zhu & Hairen Tan & Jin Xie, 2022. "Decarboxylative tandem C-N coupling with nitroarenes via SH2 mechanism," Nature Communications, Nature, vol. 13(1), pages 1-10, December.
    3. Mengjie Jiao & Jie Zhang & Minyan Wang & Hongjian Lu & Zhuangzhi Shi, 2024. "Metallaphotoredox deuteroalkylation utilizing thianthrenium salts," Nature Communications, Nature, vol. 15(1), pages 1-11, December.
    4. Zhiwei Zhao & Ranran Zhang & Yaowen Liu & Zile Zhu & Qiuyan Wang & Youai Qiu, 2024. "Electrochemical C−H deuteration of pyridine derivatives with D2O," Nature Communications, Nature, vol. 15(1), pages 1-9, December.
    5. Jonathan D. Dabbs & Caleb C. Taylor & Martin S. Holdren & Sarah E. Brewster & Brian T. Quillin & Alvin Q. Meng & Diane A. Dickie & Brooks H. Pate & W. Dean Harman, 2024. "Designing chemical systems for precision deuteration of medicinal building blocks," Nature Communications, Nature, vol. 15(1), pages 1-11, December.
    6. Yuanli Xu & Wenlong Chen & Ruihua Pu & Jia Ding & Qing An & Yi Yang & Weimin Liu & Zhiwei Zuo, 2024. "Selective monodeuteration enabled by bisphosphonium catalyzed ring opening processes," Nature Communications, Nature, vol. 15(1), pages 1-9, December.
    7. Qiang Wei & Yuhsuan Lee & Weiqiu Liang & Xiaolei Chen & Bo-shuai Mu & Xi-Yang Cui & Wangsuo Wu & Shuming Bai & Zhibo Liu, 2022. "Photocatalytic direct borylation of carboxylic acids," Nature Communications, Nature, vol. 13(1), pages 1-9, December.
    8. Justin T. Weatherford-Pratt & Jacob A. Smith & Jeremy M. Bloch & Megan N. Ericson & Jeffery T. Myers & Karl S. Westendorff & Diane A. Dickie & W. Dean Harman, 2023. "The double protonation of dihapto-coordinated benzene complexes enables dearomatization using aromatic nucleophiles," Nature Communications, Nature, vol. 14(1), pages 1-8, December.
    9. 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.
    10. Qian Zhang & Yulong Wang & Cameron Nickle & Ziyu Zhang & Andrea Leoncini & Dong-Chen Qi & Kai Sotthewes & Alessandro Borrini & Harold J. W. Zandvliet & Enrique Barco & Damien Thompson & Christian A. N, 2024. "Molecular switching by proton-coupled electron transport drives giant negative differential resistance," Nature Communications, Nature, vol. 15(1), pages 1-9, December.
    11. Xinlong Ma & Haibin Yin & Zhengtian Pu & Xinyan Zhang & Sunpei Hu & Tao Zhou & Weizhe Gao & Laihao Luo & Hongliang Li & Jie Zeng, 2024. "Propane wet reforming over PtSn nanoparticles on γ-Al2O3 for acetone synthesis," Nature Communications, Nature, vol. 15(1), pages 1-12, December.
    12. Runze Luan & Ping Lin & Kun Li & Yu Du & Weiping Su, 2024. "Remote-carbonyl-directed sequential Heck/isomerization/C(sp2)–H arylation of alkenes for modular synthesis of stereodefined tetrasubstituted olefins," Nature Communications, Nature, vol. 15(1), pages 1-10, 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:13:y:2022:i:1:d:10.1038_s41467-022-31956-3. 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.