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首页> 外文期刊>Journal of the American Chemical Society >Development and Mechanistic Interrogation of Interrupted Chain-Walking in the Enantioselective Relay Heck Reaction
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Development and Mechanistic Interrogation of Interrupted Chain-Walking in the Enantioselective Relay Heck Reaction

机译：倾向解中继反应中断链条中断链路的发展与机械讯问

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摘要

The formation of alkyl-palladium complexes via the nucleopalladation of alkenes is the entry point for a wide range of diverse reactions. One possibility is that the intermediate alkyl-Pd complexes can undergo a "chain-walking" event, to allow for remote functionalization through various termination processes. However, there are few methods to selectively interrupt the chain-walking process at a prescribed location. Herein, we demonstrate that a variety of homoallylic protected amines undergo an interrupted enantioselective relay Heck reaction to give enantioenriched allylic amine products. The selectivity of this process can be diverted to exclusively yield the ene-amide products by virtue of changing the nature of the amine protecting group. To rationalize this observation, we combine experiment and computation to investigate the mechanism of the chain-walking process and termination events. Isotopic labeling experiments and the computed reaction pathways suggest that the system is likely under thermodynamic control, with the selectivity being driven by the relative stability of intermediates encountered during chain-walking. These results illustrate that the chain-walking of alkyl-palladium complexes can be controlled through the alteration of thermodynamic processes and provides a roadmap for exploiting these processes in future reaction development.
机译：通过烯烃的核糖体形成烷基 - 钯配合物是各种不同反应的入口点。一种可能性是中间体烷基-Pd络合物可以经历“链步行”事件，以允许通过各种终端过程进行远程功能化。然而，很少有方法可以在规定位置选择性地中断链条行走过程。在此，我们证明了各种统一的保护胺经历了中断的对映选择性继电器Heck反应，得到对烯丙基烯丙基胺产物。该方法的选择性可以通过改变胺保护基团的性质而被转移以排除烯酰胺产物。为了合理化这一观察，我们将实验和计算结合起来调查链条行走过程和终止事件的机制。同位素标记实验和计算的反应途径表明该系统可能在热力学控制下，选择性受到在行走期间遇到的中间体的相对稳定性的选择性。这些结果表明，可以通过热力学过程的改变来控制烷基 - 钯配合物的链路，并提供用于利用这些过程在未来的反应开发中的路线图。

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  • 来源
    《Journal of the American Chemical Society》 |2020年第23期|10516-10525|共10页
  • 作者

    Sean P. Ross; Ajara A. Rahman; Matthew S. Sigman;

  • 作者单位

    Department of Chemistry University of Utah Salt Lake City Utah 84112 United States;

    Department of Chemistry University of Utah Salt Lake City Utah 84112 United States;

    Department of Chemistry University of Utah Salt Lake City Utah 84112 United States;

  • 收录信息 美国《科学引文索引》(SCI);美国《工程索引》(EI);美国《生物学医学文摘》(MEDLINE);美国《化学文摘》(CA);
  • 原文格式 PDF
  • 正文语种 eng
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