Aug 05，2025

Congrats to Lili Shao, Zeikai Fang, et al. for the latest publication in Nat. Commun. In this work, We have developed a dinuclear copper-catalyzed asymmetric [3+2] annulation between tertiary propargylic carbonates and diverse C,O-bisnucleophiles under mild conditions, using binuclear copper catalysts supported by chiral benzo[c]cinnoline dioxazoline frameworks. The proposed mechanism demonstrates that the binuclear Cu core can plays a bifunctional role in coordinating both acetylide and allenylidene species via σ and π interactions. Potential dinuclear synergy positions the electrophilic site of the copper-allenylidene intermediates near the chiral pocket, facilitating stereocontrolled quaternary carbon center formation from dialkyl propargylic alcohols. This spatial arrangement overcomes inherent steric challenges in the stereoselective formation of quaternary carbons bearing dual alkyl substituents and provides mechanistic insights into cooperative dinuclear catalysis for asymmetric transformations.