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Palladium-catalyzed enantioselective dienylation of propargylic carbonates via sulfonimidamide desymmetrization

Author

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  • Changyu Xu

    (Nanjing Normal University, State Key Laboratory of Microbial Technology, Jiangsu Collaborative Innovation Center of Biomedical Functional Materials, School of Chemistry and Materials Science)

  • Jinyan Hou

    (Nanjing Normal University, State Key Laboratory of Microbial Technology, Jiangsu Collaborative Innovation Center of Biomedical Functional Materials, School of Chemistry and Materials Science)

  • Yongzhi Chen

    (Nanjing Normal University, State Key Laboratory of Microbial Technology, Jiangsu Collaborative Innovation Center of Biomedical Functional Materials, School of Chemistry and Materials Science)

  • Leyang Zhang

    (Nanjing Normal University, State Key Laboratory of Microbial Technology, Jiangsu Collaborative Innovation Center of Biomedical Functional Materials, School of Chemistry and Materials Science)

  • Chen Zhou

    (Nanjing Normal University, State Key Laboratory of Microbial Technology, Jiangsu Collaborative Innovation Center of Biomedical Functional Materials, School of Chemistry and Materials Science)

  • Xudong Chen

    (Nanjing Normal University, State Key Laboratory of Microbial Technology, Jiangsu Collaborative Innovation Center of Biomedical Functional Materials, School of Chemistry and Materials Science)

  • Liang-An Chen

    (Nanjing Normal University, State Key Laboratory of Microbial Technology, Jiangsu Collaborative Innovation Center of Biomedical Functional Materials, School of Chemistry and Materials Science
    Nanjing University, State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering)

Abstract

Asymmetric transition metal-catalyzed nucleophilic substitution of propargylic electrophiles is a powerful method for furnishing enantiomerically enriched molecules. However, catalytic enantioselective dienylation remains a significant challenge due to the lack of effective strategies for asymmetric induction and the difficulty in simultaneously controlling regio-, chemo-, and stereoselectivity. Herein, we report a palladium-catalyzed enantioselective dienylation of propargylic carbonates, enabled by a sulfonimidamide desymmetrization strategy that utilizes ion-pairing and ligand-bite-angle control. Notably, smaller-bite-angle ligands facilitate tight ion-pair formation between the cationic allenyl-Pd complex and sulfonimidamide anion, steering regioselectivity toward C2-dienylation. Leveraging this ion-pairing and ligand-directed mechanism enhances proximity and orientation effects between the prochiral sulfonimidamide anion and adjacent reactive C2-Site of the allenyl-Pd complex, enabling precise tuning of the chiral pocket around palladium center. This study demonstrates that ligand bite angle-directed counteranion positioning in cationic transition metal catalysis can serve as a general strategy for addressing challenging selectivity issues in asymmetric synthesis.

Suggested Citation

  • Changyu Xu & Jinyan Hou & Yongzhi Chen & Leyang Zhang & Chen Zhou & Xudong Chen & Liang-An Chen, 2025. "Palladium-catalyzed enantioselective dienylation of propargylic carbonates via sulfonimidamide desymmetrization," Nature Communications, Nature, vol. 16(1), pages 1-13, December.
    • Handle: RePEc:nat:natcom:v:16:y:2025:i:1:d:10.1038_s41467-025-65132-0
    DOI: 10.1038/s41467-025-65132-0
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    References listed on IDEAS

    as
    1. Zheng-Lin Wang & Rong Zhu, 2025. "Controlled chain-growth polymerization via propargyl/allenyl palladium intermediates," Nature Communications, Nature, vol. 16(1), pages 1-8, December.
    2. Jiayin Zhang & Xihao Chang & Xianghong Xu & Hongyi Wang & Lingzi Peng & Chang Guo, 2022. "Nickel-catalyzed switchable 1,3-dienylation and enantioselective allenylation of phosphine oxides," Nature Communications, Nature, vol. 13(1), pages 1-11, December.
    3. Xin Huang & Shangze Wu & Wangteng Wu & Pengbin Li & Chunling Fu & Shengming Ma, 2016. "Palladium-catalysed formation of vicinal all-carbon quaternary centres via propargylation," Nature Communications, Nature, vol. 7(1), pages 1-8, November.
    4. John M. Ovian & Petra Vojáčková & Eric N. Jacobsen, 2023. "Enantioselective transition-metal catalysis via an anion-binding approach," Nature, Nature, vol. 616(7955), pages 84-89, April.
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