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Heavier Group 2 Metals and Intermolecular Hydroamination: A Computational and Synthetic Assessment

机译:重金属2和分子间氢胺化:计算和综合评估

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摘要

We have recently demonstrated that catalytic intramolecular hydroamination of aminoalkenes may be achieved through use of the d~o metals of group 2 (Scheme 1). In common with other metal-mediated transformations, the effect of ionic radius on reaction kinetics in organolanthanide(III) hydroamination catalysis is well-documented, and the reaction tends to proceed at lower rates with decreasing metal ionic radius. This effect has been ascribed to the greater degree of coordinative saturation at the electrophilic metal center, increasing the energy of the transition state of the rate-determining alkene insertion step.
机译:我们最近证明,通过使用第2族的d-o金属可以实现氨基烯烃的分子内催化氢化胺化(方案1)。与其他金属介导的转化一样,离子半径对有机镧系元素(III)加氢胺化催化反应动力学的影响已得到充分证明,并且随着金属离子半径的减小,反应倾向于以较低的速率进行。该效应归因于亲电子金属中心处更大的配位饱和度,从而增加了决定速率的烯烃插入步骤的过渡态的能量。

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  • 来源
    《Journal of the American Chemical Society》 |2009年第36期|12906-12907|共2页
  • 作者单位

    Department of Chemistry, Imperial College London, Exhibition Road, South Kensington, London SW7 2AZ, U.K.;

    Department of Chemistry, Imperial College London, Exhibition Road, South Kensington, London SW7 2AZ, U.K.;

    Department of Chemistry, Imperial College London, Exhibition Road, South Kensington, London SW7 2AZ, U.K.;

    Department of Chemistry, University of Bath, Claverton Down, Bath BA2 7AY, U.K.;

    Department of Chemistry, Imperial College London, Exhibition Road, South Kensington, London SW7 2AZ, U.K.;

    GlaxoSmithKline Medicines Research Centre, Gunnels Wood Road, Stevenage, Hertfordshire SG1 2NY, U.K.;

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  • 原文格式 PDF
  • 正文语种 eng
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  • 入库时间 2022-08-18 03:17:16

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