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Metal-free photoinduced C(sp3)–H/C(sp3)–H cross-coupling to access α‑tertiary amino acid derivatives

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Listed:
  • Yujun Li

    (Sichuan University)

  • Shaopeng Guo

    (Southwest Minzu University)

  • Qing-Han Li

    (Southwest Minzu University)

  • Ke Zheng

    (Sichuan University)

Abstract

The cross-dehydrogenative coupling (CDC) reaction is the most direct and efficient method for constructing α-tertiary amino acids (ATAAs), which avoids the pre-activation of C(sp3)-H substrates. However, the use of transition metals and harsh reaction conditions are still significant challenges for these reactions that urgently require solutions. This paper presents a mild, metal-free CDC reaction for the construction of ATAAs, which is compatible with various benzyl C-H substrates, functionalized C-H substrates, and alkyl substrates, with good regioselectivity. Notably, our method exhibits excellent functional group tolerance and late-stage applicability. According to mechanistic studies, the one-step synthesized and bench-stable N-alkoxyphtalimide generates a highly electrophilic trifluoro ethoxy radical that serves as a key intermediate in the reaction process and acts as a hydrogen atom transfer reagent. Therefore, our metal-free and additive-free method offers a promising strategy for the synthesis of ATAAs under mild conditions.

Suggested Citation

  • Yujun Li & Shaopeng Guo & Qing-Han Li & Ke Zheng, 2023. "Metal-free photoinduced C(sp3)–H/C(sp3)–H cross-coupling to access α‑tertiary amino acid derivatives," Nature Communications, Nature, vol. 14(1), pages 1-9, December.
    • Handle: RePEc:nat:natcom:v:14:y:2023:i:1:d:10.1038_s41467-023-41956-6
    DOI: 10.1038/s41467-023-41956-6
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    References listed on IDEAS

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    1. John J. Murphy & David Bastida & Suva Paria & Maurizio Fagnoni & Paolo Melchiorre, 2016. "Asymmetric catalytic formation of quaternary carbons by iminium ion trapping of radicals," Nature, Nature, vol. 532(7598), pages 218-222, April.
    2. Isabelle Nathalie-Marie Leibler & Makeda A. Tekle-Smith & Abigail G. Doyle, 2021. "A general strategy for C(sp3)–H functionalization with nucleophiles using methyl radical as a hydrogen atom abstractor," Nature Communications, Nature, vol. 12(1), pages 1-10, December.
    3. James D. Cuthbertson & David W. C. MacMillan, 2015. "The direct arylation of allylic sp3 C–H bonds via organic and photoredox catalysis," Nature, Nature, vol. 519(7541), pages 74-77, March.
    4. Kaizhi Li & Qian Wu & Jingbo Lan & Jingsong You, 2015. "Coordinating activation strategy for C(sp3)–H/C(sp3)–H cross-coupling to access β-aromatic α-amino acids," Nature Communications, Nature, vol. 6(1), pages 1-9, December.
    5. 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.
    6. Chao Shu & Adam Noble & Varinder K. Aggarwal, 2020. "Metal-free photoinduced C(sp3)–H borylation of alkanes," Nature, Nature, vol. 586(7831), pages 714-719, October.
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