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首页> 外文学位 >Silylene and germylene activation of alkane, ether and amine carbon-hydrogen bonds mediated by an aryl halide. Observation of an aryl halide kinetic isotope effect for the carbon-hydrogenactivation reaction.
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Silylene and germylene activation of alkane, ether and amine carbon-hydrogen bonds mediated by an aryl halide. Observation of an aryl halide kinetic isotope effect for the carbon-hydrogenactivation reaction.

机译：芳基卤化物介导的烷烃，醚和胺的碳氢键的亚甲硅烷基和亚二甲基苯活化。碳-氢活化反应的芳基卤化物动力学同位素效应的观察。

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摘要

Two new types reactions capable of activation the C-H bond a to nitrogen are reported. The silylene [(CH)2tBu2N 2]Si (1) was found to activate the weakest C-H bond of alkanes, ethers or amines when combined with an equivalent of an aryl halide. A competing reaction pathway to the C-H activation is oxidative addition of the aryl halide to 1, dilution techniques were used for reducing the percentage of oxidative addition product formed. Additionally, the germeylene [TMS 2HC]2Ge (21) was also observed to C-H activate amines when combined with an aryl halide. Amine substrate with C(sp 3)-H bonds alpha and beta to the amine nitrogen atom demonstrate different reactivity with 1/Ph-I and 21/Ph-I. For example, reacting Et3N with 1/Ph-I forms the single C-H activation product [(CH)2tBu2N 2]Si(I)[CH(CH3)NEt2] (7), a small percentage of [(CH)2tBu2N2]Si(I)(Ph) (2) and [(CH)2tBu2N 2]Si(H)(NEt2) (8). In contrast, reacting Et 3N with 21/Ph-I results in quantitative formation of [TMS 2HC]2Ge(I)(H) (27). Independent synthesis of 8, or 27, was achieved by reacting 1, or 21, in Et3N with [Et3NH]I, implying in situ formation of [Et3NH]I.;Deuterium labeled compounds were used for gaining a better understanding of the rate-determining step. The silylene C-H activation reaction of Et 2O was found to have a KIE of 5.7 + 0.1, a magnitude consistent with the C-H bond breaking at or before the rate-determining step. Additionally, the C-H activation of Et2O with 1/Ph-X or 21 /Ph-X resulted in a KIE for the protons of the aryl halide. The KIEs of the aryl group range from a low of 1.1 +/- 0.1 for 1/4-C 6H4DI to high of 1.7 +/- 0.1 for 21/C6D5Br. The aryl KIEs are consistent with the Ar-X bond breaking at or before the rate-determining step.
机译：报道了两种能够激活C-H键与氮原子结合的新型反应。发现亚甲硅烷基[（CH）2tBu2N 2] Si（1）与当量的芳基卤化物结合时，可活化烷烃，醚或胺的最弱C-H键。 C-H活化的竞争反应途径是将芳基卤化物氧化加成1，使用稀释技术来减少形成的氧化加成产物的百分比。此外，还观察到与亚芳基卤化物结合时，the烯[TMS 2HC] 2Ge（21）具有C-H活化胺。具有C（sp 3）-H键与胺氮原子的α和β键的胺底物表现出与1 / Ph-1和21 / Ph-1的不同反应性。例如，使Et3N与1 / Ph-I反应形成单一的CH活化产物[（CH）2tBu2N 2] Si（I）[CH（CH3）NEt2]（7），即少量的[（CH）2tBu2N2] Si （I）（Ph）（2）和[（CH）2tBu2N 2] Si（H）（NEt2）（8）。相反，Et 3N与21 / Ph-I反应导致定量形成[TMS 2HC] 2Ge（I）（H）（27）。通过使1或21在Et3N中与[Et3NH] I反应，可以独立合成8或27，这意味着[Et3NH] I的原位形成。确定步骤。发现Et 2O的甲硅烷基C-H活化反应的KIE为5.7 + 0.1，其大小与速率确定步骤或之前的C-H键断裂一致。此外，用1 / Ph-X或21 / Ph-X对Et2O进行C-H活化会产生芳基卤的质子的KIE。芳基的KIE范围从对于1 / 4-C 6H4DI的1.1 +/- 0.1的低到对于21 / C6D5Br的1.7 +/- 0.1的高。芳基KIE与在速率确定步骤或之前的Ar-X键断裂一致。

著录项

  • 作者

    Walker, Randon H.;

  • 作者单位

    University of Michigan.;

  • 授予单位 University of Michigan.;
  • 学科 Chemistry Organic.
  • 学位 Ph.D.
  • 年度 2009
  • 页码 105 p.
  • 总页数 105
  • 原文格式 PDF
  • 正文语种 eng
  • 中图分类
  • 关键词

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