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Catalytic enantioselective construction of axial chirality in 1,3-disubstituted allenes

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  • Shihua Song

    (Zhejiang University)

  • Jing Zhou

    (Zhejiang University)

  • Chunling Fu

    (Zhejiang University)

  • Shengming Ma

    (Zhejiang University)

Abstract

Metal-catalyzed enantioselective construction of the loosening axial allene chirality spreading over three carbon atoms using a chiral ligand is still a significant challenge. In the literature, steric effect of the substrates is the major strategy applied for such a purpose. Herein, we present a general palladium-catalyzed asymmetrization of readily available racemic 2,3-allenylic carbonates with different types of non-substituted and 2-substituted malonates using (R)-(−)-DTBM-SEGPHOS as the preferred ligand to afford 1,3-disubstituted chiral allenes with 90~96% ee. This protocol has been applied to the first enantioselective synthesis of natural product, (R)-traumatic lactone. Control experiments showed that in addition to the chiral ligand, conducting this transformation via Procedure C, which excludes the extensive prior coordination of the allene unit in the starting allene with Pd forming a species without the influence of the chiral ligand, is crucial for the observed high enantioselectivity.

Suggested Citation

  • Shihua Song & Jing Zhou & Chunling Fu & Shengming Ma, 2019. "Catalytic enantioselective construction of axial chirality in 1,3-disubstituted allenes," Nature Communications, Nature, vol. 10(1), pages 1-9, December.
    • Handle: RePEc:nat:natcom:v:10:y:2019:i:1:d:10.1038_s41467-018-07908-1
    DOI: 10.1038/s41467-018-07908-1
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    Cited by:

    1. Chang You & Mingying Shi & Xueling Mi & Sanzhong Luo, 2023. "Asymmetric α-allylic allenylation of β-ketocarbonyls and aldehydes by synergistic Pd/chiral primary amine catalysis," Nature Communications, Nature, vol. 14(1), pages 1-7, December.
    2. Qi Liu & Jian Zheng & Xue Zhang & Shengming Ma, 2022. "Photo and copper dual catalysis for allene syntheses from propargylic derivatives via one-electron process," Nature Communications, Nature, vol. 13(1), pages 1-10, December.

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