首页> 外文期刊>European journal of mass spectrometry >Investigation of coordination of Mg(II) cations to 2-pyrimidinyloxy-N- arylbenzylamines by electrospray mass spectrometry: Insights for Mg(II) catalyzed Smiles rearrangement reactions
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Investigation of coordination of Mg(II) cations to 2-pyrimidinyloxy-N- arylbenzylamines by electrospray mass spectrometry: Insights for Mg(II) catalyzed Smiles rearrangement reactions

机译:通过电喷雾质谱研究Mg(II)阳离子与2-嘧啶氧基-N-芳基苄基胺的配位:Mg(II)催化的Smiles重排反应的见解

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摘要

The CH_3OH solutions of pyrimidinyloxy-N-arylbenzylamines (1-5) in the presence of Mg(II)X_2 salts (X = Cl or ClO_4) were investigated by electrospray ionization mass spectrometry and tandem mass spectrometry (MS/MS) subsequently, showing that the cationic Mg(II) complexes 1-5·MgX~+ were important active complexes or intermediates for initiating interesting Smiles rearrangement reactions in both the gas- and solution phases. By using different MgX_2 salts and selecting a set of reactants with different substitutes, the role of the counter-ion (X ~-) and the structure effect of the reactants on the Mg(II) catalyzed Smiles rearrangement reactions were studied. Moreover, the solvent effect on Mg(II) catalyzed Smiles rearrangement reactions was revealed by studying the CH_3OH adduct complexes of 1-5·MgCl~+, which showed that the coordination of CH_3OH to the Mg(II) center in the complexes decreased the reaction tendency. The mechanisms involved in the gas-phase Mg(II) catalyzed Smiles rearrangement reactions were proposed on the basis of MS/MS experiments and theoretical computations, showing some unique chemistries initiated by introducing Mg(II) into the template molecules.
机译:通过电喷雾电离质谱和串联质谱(MS / MS)研究了在Mg(II)X_2盐(X = Cl或ClO_4)存在下的嘧啶基氧基-N-芳基苄基胺(1-5)的CH_3OH溶液阳离子Mg(II)配合物1-5·MgX〜+是重要的活性配合物或中间体,可在气相和溶液相中引发有趣的Smiles重排反应。通过使用不同的MgX_2盐并选择一组具有不同取代基的反应物,研究了抗衡离子(X〜-)的作用以及反应物对Mg(II)催化的Smiles重排反应的结构作用。此外,通过研究1-5·MgCl〜+的CH_3OH加合物,揭示了溶剂对Mg(II)催化Smiles重排反应的影响,表明CH_3OH与Mg(II)中心的配位降低了反应趋势。在MS / MS实验和理论计算的基础上,提出了气相Mg(II)催化的Smiles重排反应所涉及的机理,显示了通过将Mg(II)引入模板分子而引发的一些独特的化学反应。

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