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Site- and enantioselective cross-coupling of saturated N-heterocycles with carboxylic acids by cooperative Ni/photoredox catalysis

Author

Listed:
  • Xiaomin Shu

    (College of Chemistry and Chemical Engineering, Xiamen University)

  • De Zhong

    (College of Chemistry and Chemical Engineering, Xiamen University)

  • Qian Huang

    (College of Chemistry and Chemical Engineering, Xiamen University)

  • Leitao Huan

    (College of Chemistry and Chemical Engineering, Xiamen University)

  • Haohua Huo

    (College of Chemistry and Chemical Engineering, Xiamen University)

Abstract

Site- and enantioselective cross-coupling of saturated N-heterocycles and carboxylic acids—two of the most abundant and versatile functionalities—to form pharmaceutically relevant α-acylated amine derivatives remains a major challenge in organic synthesis. Here, we report a general strategy for the highly site- and enantioselective α-acylation of saturated N-heterocycles with in situ-activated carboxylic acids. This modular approach exploits the hydrogen-atom-transfer reactivity of photocatalytically generated chlorine radicals in combination with asymmetric nickel catalysis to selectively functionalize cyclic α-amino C−H bonds in the presence of benzylic, allylic, acyclic α-amino, and α-oxy methylene groups. The mild and scalable protocol requires no organometallic reagents, displays excellent chemo-, site- and enantioselectivity, and is amenable to late-stage diversification, including a modular synthesis of previously inaccessible Taxol derivatives. Mechanistic studies highlight the exceptional versatility of the chiral nickel catalyst in orchestrating (i) catalytic chlorine elimination, (ii) alkyl radical capture, (iii) cross-coupling, and (iv) asymmetric induction.

Suggested Citation

  • Xiaomin Shu & De Zhong & Qian Huang & Leitao Huan & Haohua Huo, 2023. "Site- and enantioselective cross-coupling of saturated N-heterocycles with carboxylic acids by cooperative Ni/photoredox catalysis," Nature Communications, Nature, vol. 14(1), pages 1-10, December.
  • Handle: RePEc:nat:natcom:v:14:y:2023:i:1:d:10.1038_s41467-023-35800-0
    DOI: 10.1038/s41467-023-35800-0
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    References listed on IDEAS

    as
    1. Peter C. St. John & Yanfei Guan & Yeonjoon Kim & Seonah Kim & Robert S. Paton, 2020. "Prediction of organic homolytic bond dissociation enthalpies at near chemical accuracy with sub-second computational cost," Nature Communications, Nature, vol. 11(1), pages 1-12, December.
    2. Xiaokai Cheng & Huangzhe Lu & Zhan Lu, 2019. "Enantioselective benzylic C–H arylation via photoredox and nickel dual catalysis," Nature Communications, Nature, vol. 10(1), pages 1-7, December.
    3. Geun Seok Lee & Beomsoon Park & Soon Hyeok Hong, 2022. "Stereoretentive cross-coupling of chiral amino acid chlorides and hydrocarbons through mechanistically controlled Ni/Ir photoredox catalysis," Nature Communications, Nature, vol. 13(1), pages 1-11, December.
    4. Peter C. John & Yanfei Guan & Yeonjoon Kim & Seonah Kim & Robert S. Paton, 2020. "Publisher Correction: Prediction of organic homolytic bond dissociation enthalpies at near chemical accuracy with sub-second computational cost," Nature Communications, Nature, vol. 11(1), pages 1-3, December.
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