Zirconium- and silicon-containing intermediates with three fused rings in a zirconocene-mediated intermolecular coupling reaction.
Zirconium- and silicon-containing intermediates with three fused rings in a zirconocene-mediated intermolecular coupling reaction.
复制标题
DOI：
10.1002/anie.200903329
复制
发表时间：
2009-09
影响因子：
--
通讯作者：
Wen‐Xiong Zhang;Shaoguang Zhang;Xiaohua Sun;M. Nishiura;Z. Hou;Z. Xi
中科院分区：
文献类型：
--
作者：
Wen‐Xiong Zhang;Shaoguang Zhang;Xiaohua Sun;M. Nishiura;Z. Hou;Z. Xi
过渡金属介导的反应中重要中间体的分离和反应活性是有机金属和合成有机化学的研究热点。对这些中间体的研究不仅对深入理解看似复杂的反应机理具有重要作用，而且还可能导致发现新的合成有用的反应。我们报道了一个硅基系联二炔分子与三个有机腈分子的锆茂分子间偶联反应，反应混合物[式(1)]水解后得到吡咯[3，2-c]吡啶衍生物(5-氮杂环)。[1，2]上述一锅反应最有趣的特点是五个组分以一种未知的途径以完美的选择性结合在一起，这促使我们去研究到底发生了什么。[3]我们预计可能涉及到新的和重要的反应模式。事实上，我们现在终于发现，将所有五个组分结合在一起的过程是非常不寻常的，不可预测的，并且对涉及CN三元裂解的金属中介反应具有普遍重要性
The isolation and reactivity of important intermediates in transition-metal-mediated reactions are of interest in both organometallic and synthetic organic chemistry. Studies of these intermediates not only play an important role in the indepth understanding of seemingly complicated reaction mechanisms, but can also lead to the discovery of new synthetically useful reactions. We have reported a zirconocene-mediated intermolecular coupling reaction of one molecule of a silyl-tethered diyne with three molecules of organonitriles, which afforded pyrrolo [3, 2-c] pyridine derivatives (5-azaindoles) upon hydrolysis of the reaction mixture [Eq.(1)].[1, 2]The most interesting feature of this above one-pot reaction is that five components are involved and integrated in a perfect selective manner via an unknown pathway, which tempted us to investigate what is really going on.[3] We anticipated that novel and important reaction patterns might be involved. Indeed, we have now finally discovered that the process that combines all the five components together is very unusual, unpredictable, and of general importance to metalmediated reactions involving the cleavage of CN triple