College of Chemistry and Molecular Sciences, The Institute for Advanced Studies (IAS), Wuhan University, Wuhan, Hubei 430072, China.
School of Chemistry and Chemical Engineering, Chongqing University, Chongqing 400030, China.
Nat Commun. 2017 Mar 16;8:14794. doi: 10.1038/ncomms14794.
As a versatile metal, copper has demonstrated a wide application in acting as both organometallic reagent and catalyst. Organocuprates are among the most used organometallic reagents in the formation of new carbon-carbon bonds in organic synthesis. Therefore, revealing the real structures of organocuprates in solution is crucial to provide insights into the reactivity of organocuprates. Here we provide several important insights into organocuprate chemistry. The main finding contains the following aspects. The Cu(0) particles were detected via the reduction of CuX by nBuLi or PhLi. The Cu(II) precursors CuX (X=Cl, Br) could be used for the preparation of Gilman reagents. In addition, we provide direct evidence for the role and effect of LiX in organocuprate synthesis. Moreover, the EXAFS spectrum provides direct evidence for the exact structure of Li CuX ate complex in solution. This work not only sheds important light on the role of LiX in the formation of organocuprates but also reports two new routes for organocuprate synthesis.
作为一种多功能金属，铜已被证明在作为有机金属试剂和催化剂方面有广泛的应用。有机铜试剂是有机合成中新的碳-碳键形成中最常用的有机金属试剂之一。因此，揭示有机铜试剂在溶液中的真实结构对于了解有机铜试剂的反应性至关重要。在这里，我们提供了一些关于有机铜化学的重要见解。主要发现包括以下几个方面。通过 nBuLi 或 PhLi 将 CuX 还原检测到 Cu(0)颗粒。Cu(II)前体 CuX(X=Cl、Br)可用于制备吉尔曼试剂。此外，我们还为 LiX 在有机铜试剂合成中的作用和影响提供了直接证据。此外，EXAFS 光谱为溶液中 LiCuXate 配合物的确切结构提供了直接证据。这项工作不仅阐明了 LiX 在有机铜试剂形成中的作用，还报道了两种新的有机铜试剂合成途径。
