上海科技大学知识管理系统

Despite binuclear Cu active sites present in some biological and heterogeneous catalysts, the development of chiral binuclear copper catalysts is still in its infancy and remains a formidable challenge. A notable example is that the asymmetric propargylic substitution catalyzed by a chiral binuclear Cu complex is still unknown, although some kinds of in -situ -assembled binuclear Cu species have frequently been proposed as active intermediates. Herein, we report a series of binuclear copper catalysts supported by chiral benzo [c] cinnoline dioxazoline frameworks, which demonstrated high efficiency in (dynamic) kinetic resolution of propargylic alcohol derivatives via propargylic substitution. Mechanistic investigations suggested that the binuclear Cu core shows a bifunctional role in coordination with acetylide and allenylidene ligands. These findings shed light onto the long-standing mechanistic ambiguity, providing solid support for the proposal that the binuclear Cu core can be crucial for substrate activation and selectivity control in catalysis.