Palladium-catalyzed enantioselective dienylation of propargylic carbonates via sulfonimidamide desymmetrization.

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. Lever

SUBMITTER: Xu C 

PROVIDER: S-EPMC12639056 | biostudies-literature | 2025 Nov

REPOSITORIES: biostudies-literature