Copper-catalyzed Huisgen and oxidative Huisgen coupling reactions controlled by polysiloxane-supported amines (AFPs) for the divergent synthesis of triazoles and bistriazoles.
Copper-catalyzed Huisgen and oxidative Huisgen coupling reactions controlled by polysiloxane-supported amines (AFPs) for the divergent synthesis of triazoles and bistriazoles.
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DOI：
10.1002/chem.201202472
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发表时间：
2012-10
期刊：
影响因子：
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通讯作者：
Zhanjiang Zheng;F. Ye;Long‐Sheng Zheng;Ke-Fang Yang;G. Lai;Li‐Wen Xu
中科院分区：
文献类型：
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作者：
Zhanjiang Zheng;F. Ye;Long‐Sheng Zheng;Ke-Fang Yang;G. Lai;Li‐Wen Xu
一个有趣的例子发散催化与铜（I）和胺官能化的大分子聚硅氧烷系统中成功地提出了点击化学。在这篇手稿中，我们证明了显着的能力，仲胺官能的聚硅氧烷诱导氧化偶联在铜介导的Huisgen反应的叠氮化物和炔，从而实现良好的产率和选择性。由聚硅氧烷负载的仲胺介导的点击反应允许制备新的杂环化合物，即双三唑。相比之下，还令人惊讶的是，使用二胺官能聚硅氧烷作为配体以优异的产率导致经典的Huisgen [3+2]环加成。从现有的胺官能化聚硅氧烷控制的Huisgen反应或氧化Huisgen偶联反应对不同产物的结果和提出的机理，我们认为，由仲胺官能化聚硅氧烷稳定和分散的单核双三唑-铜配合物有利于普及氧化偶联途径。
An interesting example of a divergent catalysis with a copper(I) and amine-functional macromolecular polysiloxanes system was successfully presented in click chemistry. In this manuscript, we demonstrate the remarkable ability of the secondary amine-functional polysiloxane to induce oxidative coupling in the copper-mediated Huisgen reactions of azides and alkynes, thereby achieving good yields and selectivities. The click reactions mediated by a polysiloxane-supported secondary amine allow the preparation of novel heterocyclic compounds, that is, bistriazoles. Comparably, it is also surprising that the use of a diamine-functional polysiloxane as ligand led to a classic Huisgen [3+2] cycloaddition in excellent yields. From the results of the present amine-functional polysiloxanes-controlled Huisgen reaction or oxidative Huisgen coupling reaction to divergent products and the proposed mechanism, we suggested that the mononuclear bistriazole-copper complex stabilized and dispersed by the secondary amine-functional polysiloxane was beneficial to prevalent the way to oxidative coupling.