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Metallaphotoredox deuteroalkylation utilizing thianthrenium salts

Author

Listed:
  • Mengjie Jiao

    (Nanjing University)

  • Jie Zhang

    (Nanjing University)

  • Minyan Wang

    (Nanjing University)

  • Hongjian Lu

    (Nanjing University)

  • Zhuangzhi Shi

    (Nanjing University)

Abstract

Deuterium labeling compounds play a crucial role in organic and pharmaceutical chemistry. The synthesis of such compounds typically involves deuterated building blocks, allowing for the incorporation of deuterium atoms and functional groups into a target molecule in a single step. Unfortunately, the limited availability of synthetic approaches to deuterated synthons has impeded progress in this field. Here, we present an approach utilizing alkyl-substituted thianthrenium salts that efficiently and selectively introduce deuterium at the α position of alkyl chains through a pH-dependent HIE process, using D2O as the deuterium source. The resulting α-deuterated alkyl thianthrenium salts, which bear two deuterium atoms, exhibit excellent selectivity and deuterium incorporation in electrophilic substitution reactions. Through in situ formation of isotopically labelled alkyl halides, these thianthrenium salts demonstrate excellent compatibility in a series of metallaphotoredox cross-electrophile coupling with (hetero)aryl, alkenyl, alkyl bromides, and other alkyl thianthrenium salts. Our technique allows for a wide range of substrates, high deuterium incorporation, and precise control over the site of deuterium insertion within a molecule such as the benzyl position, allylic position, or any alkyl chain in between, as well as neighboring heteroatoms. This makes it invaluable for synthesizing various deuterium-labeled compounds, especially those with pharmaceutical significance.

Suggested Citation

  • 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.
  • Handle: RePEc:nat:natcom:v:15:y:2024:i:1:d:10.1038_s41467-024-48590-w
    DOI: 10.1038/s41467-024-48590-w
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    References listed on IDEAS

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    1. Dylan E. Holst & Diana J. Wang & Min Ji Kim & Ilia A. Guzei & Zachary K. Wickens, 2021. "Aziridine synthesis by coupling amines and alkenes via an electrogenerated dication," Nature, Nature, vol. 596(7870), pages 74-79, August.
    2. Cheng Chen & Zheng-Jun Wang & Hongjian Lu & Yue Zhao & Zhuangzhi Shi, 2021. "Generation of non-stabilized alkyl radicals from thianthrenium salts for C–B and C–C bond formation," Nature Communications, Nature, vol. 12(1), pages 1-9, December.
    3. Pengfei Li & Chengcheng Guo & Siyi Wang & Dengke Ma & Tian Feng & Yanwei Wang & Youai Qiu, 2022. "Facile and general electrochemical deuteration of unactivated alkyl halides," Nature Communications, Nature, vol. 13(1), pages 1-8, December.
    4. Robert W. Pipal & Kenneth T. Stout & Patricia Z. Musacchio & Sumei Ren & Thomas J. A. Graham & Stefan Verhoog & Liza Gantert & Talakad G. Lohith & Alexander Schmitz & Hsiaoju S. Lee & David Hesk & Eri, 2021. "Metallaphotoredox aryl and alkyl radiomethylation for PET ligand discovery," Nature, Nature, vol. 589(7843), pages 542-547, January.
    5. 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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