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 -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.

中文翻译：

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对映选择性炔丙基取代中明确的手性双核铜配合物：对于双核机制的长期假设


尽管一些生物和多相催化剂中存在双核铜活性位点，但手性双核铜催化剂的开发仍处于起步阶段，仍然是一个艰巨的挑战。一个值得注意的例子是，尽管某些种类的组装双核铜物种经常被提议作为活性中间体，但手性双核铜配合物催化的不对称炔丙基取代仍然未知。在此，我们报道了一系列由手性苯并[c]肉啉二恶唑啉骨架支撑的双核铜催化剂，该催化剂通过炔丙取代证明了在（动态）动力学拆分炔丙醇衍生物方面的高效率。机理研究表明，双核铜核在与乙炔化物和丙二烯配体配合中表现出双功能作用。这些发现揭示了长期存在的机制模糊性，为双核铜核对于催化中的底物活化和选择性控制至关重要的提议提供了坚实的支持。