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A theoretical study of dirhodium-catalyzed intramolecular aliphatic C-H bond amination of aryl azides

机译：芳族催化分子内脂族脂族C-H键胺化的理论研究芳基叠氮

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摘要

Dirhodium-contained catalysts mediated aliphatic C-H bond amination of aryl azides were studied using BPW91 functional. Calculations show the reactions with Rh-2(esp)(2) (esp = alpha,alpha,alpha',alpha'-tetramethyl-1,3-benzenedipropionic acid) and the model compound Rh-2(OCHO)(4) as catalysts take place via similar mechanisms. Firstly, the dirhodium metal complex coordinates with the substrate and releases nitrogen gas. This rate-determining step results in the formation of the metal nitrene. Metal nitrene mediated intramolecular C-H bond amination is conducted via two alternative pathways, respectively. The singlet metal nitrene mediated intramolecular C-H bond amination occurs via a concerted and asynchronous pathway involving direct metal nitrene insertion into the C-H bond. The triplet metal nitrene case is a stepwise pathway involving a hydrogen transfer and then a diradical recombination. Our study suggests the triplet H-abstraction is more favorable than the singlet one. The resulted triplet intermediate would not go through the high-barrier diradical recombination process, but across to the singlet pathway via a MECP and form the final singlet product. The tethered esp ligands in Rh-2(esp)(2) provide steric effects to constrain the substrate-catalyst compound but indicates inconspicuous influence on the mechanisms of dirhodium catalyzed aliphatic C-H bond amination of aryl azides.
机译：含有Dirhodium载催化剂介导的芳族脂族C-H键合芳基叠氮化物的芳族化胺化学使用BPW91官能化研究。计算显示用RH-2（ESP）（2）（ESP =α，α，α'，α-四甲基-1,3-苯并丙酸）和模型化合物RH-2（OCHO）（4）的反应。催化剂通过类似的机制进行。首先，金属金属配合物与基材坐标并释放氮气。该速率确定步骤导致金属硝酸氢。金属硝基介导的分子内C-H键合胺化通过两个替代途径进行。单态金属硝基介导的分子内C-H键合胺化通过涉及直接金属硝基插入C-H键的直接和异步途径发生。三态金属硝基壳是逐步途径，涉及氢转移，然后是Diradical重组。我们的研究表明Triplet H-Abstraction比单歌曲的抽象更有利。得到的三重态中间体不会经过高屏障的Diradical重组方法，但通过MECP穿过单线途径并形成最终单态产物。 RH-2（ESP）（2）中的系套ESP配体提供了限制基材催化剂化合物的空间效应，但表明对氨基氧化酯催化脂族C-H键胺化的机制不起眼。

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  • 来源
    《RSC Advances》 |2016年第35期|共9页
  • 作者

    Xu Huiying; Zhang Xuepeng; Ke Zhuofeng; Zhao Cunyuan;

  • 作者单位

    Sun Yat Sen Univ Sch Chem &

    Chem Engn Guangzhou 510275 Guangdong Peoples R China;

    Sun Yat Sen Univ Sch Chem &

    Chem Engn Guangzhou 510275 Guangdong Peoples R China;

    Sun Yat Sen Univ Sch Chem &

    Chem Engn Guangzhou 510275 Guangdong Peoples R China;

    Sun Yat Sen Univ Sch Chem &

    Chem Engn Guangzhou 510275 Guangdong Peoples R China;

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  • 正文语种 eng
  • 中图分类 化学;
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