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Enantioselective functionalization of unactivated C(sp3)–H bonds through copper-catalyzed diyne cyclization by kinetic resolution

Author

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  • Yang-Bo Chen

    (Xiamen University)

  • Li-Gao Liu

    (Xiamen University)

  • Zhe-Qi Wang

    (Xiamen University)

  • Rong Chang

    (Xiamen University)

  • Xin Lu

    (Xiamen University)

  • Bo Zhou

    (Xiamen University)

  • Long-Wu Ye

    (Xiamen University
    Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences)

Abstract

Site- and stereoselective C–H functionalization is highly challenging in the synthetic chemistry community. Although the chemistry of vinyl cations has been vigorously studied in C(sp3)–H functionalization reactions, the catalytic enantioselective C(sp3)–H functionalization based on vinyl cations, especially for an unactivated C(sp3)–H bond, has scarcely explored. Here, we report an asymmetric copper-catalyzed tandem diyne cyclization/unactivated C(sp3)–H insertion reaction via a kinetic resolution, affording both chiral polycyclic pyrroles and diynes with generally excellent enantioselectivities and excellent selectivity factors (up to 750). Importantly, this reaction demonstrates a metal-catalyzed enantioselective unactivated C(sp3)–H functionalization via vinyl cation and constitutes a kinetic resolution reaction based on diyne cyclization. Theoretical calculations further support the mechanism of vinyl cation-involved C(sp3)–H insertion reaction and elucidate the origin of enantioselectivity.

Suggested Citation

  • Yang-Bo Chen & Li-Gao Liu & Zhe-Qi Wang & Rong Chang & Xin Lu & Bo Zhou & Long-Wu Ye, 2024. "Enantioselective functionalization of unactivated C(sp3)–H bonds through copper-catalyzed diyne cyclization by kinetic resolution," Nature Communications, Nature, vol. 15(1), pages 1-10, December.
    • Handle: RePEc:nat:natcom:v:15:y:2024:i:1:d:10.1038_s41467-024-46288-7
    DOI: 10.1038/s41467-024-46288-7
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