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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >A comparative theoretical study of the pericyclic-pseudopericyclic character in a group of cyclizations of dienylketenes to cyclohexadienones
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A comparative theoretical study of the pericyclic-pseudopericyclic character in a group of cyclizations of dienylketenes to cyclohexadienones

机译：二烯基烯酮成环己二酮环化反应中环-伪杂环的比较理论研究

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摘要

A comprehensive B3LYP/6-31+G* study of the nature of 6 pi electrocyclizations of four different dienylketenes (2-furanyl, 2-pyrrolyl, cyclopenta-1,3-dienyl, and 2-thiophenyl-substituted ketenes) to corresponding cyclohexadienones was carried out. An analogous system ((3Z)-4-(3H-pyrrol-2-yl)buta-1,3-dien-1-one) was also analyzed. For this purpose, the complete pathways were determined (reactants, products, transition states, and the IRC connecting reactants and products), and changes in different magnetic properties (magnetic susceptibility, chi, magnetic susceptibility anisotropy, chi(anis), and the nucleus-independent chemical shifts, NICS) were monitored along the reaction profiles with a view to estimating the aromatization associated to the processes. We have also applied the ACID (anisotropy of the current-induced density) method with the same intention. The deep analysis of the results indicates a pericyclic character of the processes for the dienylketenes despite the relatively small NICS values in the transition states. Only the reaction of (3Z)-4-(3H-pyrrol-2-yl)buta-1,3-dien-1-one presents pseudopericyclic character due to the in-plane attack of the lone pair on nitrogen.
机译：全面的B3LYP / 6-31 + G *研究了四种不同的二烯基烯酮（2-呋喃基，2-吡咯基，环戊-1,3-二烯基和2-硫代苯基取代的烯酮）对相应的环己二烯酮进行6 pi电环化的性质进行了。还分析了类似的系统（（3Z）-4-（3H-吡咯-2-基）丁1,3-dien-1-one）。为此，确定了完整的路径（反应物，产物，过渡态以及IRC连接反应物和产物），并确定了不同磁特性（磁化率，磁，磁化率各向异性，chi（anis）和原子核）的变化。沿着反应曲线监测非独立化学位移（NICS），以估计与该过程相关的芳构化。我们也出于同样的目的应用了ACID（电流感应密度的各向异性）方法。对结果的深入分析表明，尽管过渡态中的NICS值相对较小，但二烯基烯酮的过程具有周环特征。由于（3Z）-4-（3H-吡咯-2-基）buta-1,3-dien-1-one的反应由于在氮原子上的孤对的面内攻击而呈现出伪周环特性。

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