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Palladium-catalyzed regio- and enantioselective migratory allylic C(sp3)-H functionalization

Author

Listed:
  • Ye-Wei Chen

    (University of Chinese Academy of Sciences
    ShanghaiTech University)

  • Yang Liu

    (University of Chinese Academy of Sciences)

  • Han-Yu Lu

    (University of Chinese Academy of Sciences
    ShanghaiTech University)

  • Guo-Qiang Lin

    (University of Chinese Academy of Sciences
    ShanghaiTech University)

  • Zhi-Tao He

    (University of Chinese Academy of Sciences)

Abstract

Transition metal-catalyzed asymmetric allylic substitution with a suitably pre-stored leaving group in the substrate is widely used in organic synthesis. In contrast, the enantioselective allylic C(sp3)-H functionalization is more straightforward but far less explored. Here we report a catalytic protocol for the long-standing challenging enantioselective allylic C(sp3)-H functionalization. Through palladium hydride-catalyzed chain-walking and allylic substitution, allylic C-H functionalization of a wide range of acyclic nonconjugated dienes is achieved in high yields (up to 93% yield), high enantioselectivities (up to 98:2 er), and with 100% atom efficiency. Exploring the reactivity of substrates with varying pKa values uncovers a reasonable scope of nucleophiles and potential factors controlling the reaction. A set of efficient downstream transformations to enantiopure skeletons showcase the practical value of the methodology. Mechanistic experiments corroborate the PdH-catalyzed asymmetric migratory allylic substitution process.

Suggested Citation

  • Ye-Wei Chen & Yang Liu & Han-Yu Lu & Guo-Qiang Lin & Zhi-Tao He, 2021. "Palladium-catalyzed regio- and enantioselective migratory allylic C(sp3)-H functionalization," Nature Communications, Nature, vol. 12(1), pages 1-9, December.
    • Handle: RePEc:nat:natcom:v:12:y:2021:i:1:d:10.1038_s41467-021-25978-6
    DOI: 10.1038/s41467-021-25978-6
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    Cited by:

    1. Yao-Xin Wang & Zhen Wang & Xiao-Hui Yang, 2024. "Palladium-catalyzed remote internal C(sp3)−H bond chlorination of alkenes," Nature Communications, Nature, vol. 15(1), pages 1-8, December.
    2. Yi-Xuan Cao & Matthew D. Wodrich & Nicolai Cramer, 2023. "Nickel-catalyzed direct stereoselective α-allylation of ketones with non-conjugated dienes," Nature Communications, Nature, vol. 14(1), pages 1-9, December.

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