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Reaction Mechanism for the LiCl-Mediated Directed Zinc Insertion: A Computational and Experimental Study

机译:LiCl介导的定向锌插入的反应机理:计算和实验研究

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In situ generation of organozinc reagents and their integration into CC bond-forming processes are of continuing interest because of the characteristically high chemo- and stereoselectivity.[1] In 2006, Knochel and co-workers discovered that the oxidative insertion of zinc dust into aryl halides is drastically accelerated in the presence of LiCl, thereby opening up a practical and efficient preparation method for aryl- and alkylzinc reagents.[2] This protocol was successfully used for chemo- and regioselective Zn insertion[3] (also termed directed ortho insertion (DoI)), and is now widely employed. Koszinowski et al. detected Li+ZnRClHal- (Hal=halide), which had been proposed by Knochel as the active species for the LiCl-mediated zinc insertion,[2] in the reaction mixture by using ESI-MS.[4,1f] However, the reaction pathway and mechanism of Li+ZnRClHal- formation are still far from being settled. Herein, we report an experimental/computational study on the LiCl-mediated zinc insertion,and we address the questions of the generation mechanism of Li+ZnRClHal, the role of LiCl, and the origin of the regioselectivity in the reaction.
机译:有机锌试剂的原位生成及其与CC键形成过程的集成一直备受关注,因为它们具有很高的化学和立体选择性。[1] 2006年,Knochel及其同事发现,在LiCl的存在下,锌粉尘进入芳基卤化物的氧化插入速度大大加快,从而开辟了一种实用而有效的制备芳基和烷基锌试剂的方法。[2]该方案已成功用于化学和区域选择性的Zn插入[3](也称为定向邻位插入(DoI)),现已广泛使用。 Koszinowski等。使用ESI-MS在反应混合物中检测到Li + ZnRClHalHal-(Hal =卤化物),这是Knochel提出的作为LiCl介导的锌插入的活性物质[2]。[4,1f] Li + ZnRClHal-形成的反应途径和机理尚待解决。在本文中,我们报告了有关LiCl介导的锌插入的实验/计算研究,并解决了Li + ZnRClHal的生成机理,LiCl的作用以及反应中区域选择性的起源的问题。

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