Palladium-catalyzed enantioselective dienylation of propargylic carbonates via sulfonimidamide desymmetrization

Changyu Xu, Jinyan Hou, Yongzhi Chen, Leyang Zhang, Chen Zhou, Xudong Chen and Liang-An Chen ()
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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

Nature Communications, 2025, vol. 16, issue 1, 1-13

Abstract: 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.

Date: 2025
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DOI: 10.1038/s41467-025-65132-0

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