Oxidation process of 1,4-dihydropyridine, 1,4-dihydropyrimidine, and pyrrolo-1,4-dihydropyrimidine: quantum chemical study

IF 2.1 4区 化学 Q3 CHEMISTRY, MULTIDISCIPLINARY Structural Chemistry Pub Date : 2024-02-07 DOI:10.1007/s11224-024-02284-7
Mariia O. Shyshkina, Serhiy M. Desenko
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Abstract

Derivatives of 1,4-dihydropyridine, 1,4-dihydropyrimidine, and its azolo analogs possess a wide range of biological activity and are involved in cellular bioenergetics. Dihydrocycles can be oxidized up to corresponding aromatic ones due to two one-electron transfers. Mechanism of the oxidation process was modeled as a stepwise change of the 1,4-dihydropyridine, 1,4-dihydropyrimidine, and pyrrolo-1,4-dihydropyrimidine using different levels of theory (Hartree–Fock, MP2, DFT), basis sets, and models of environment (vacuum approximation, PCM model describing a non-specific influence of polarizing environment, or PCM model with an explicit water molecule describing both non-specific and specific influence of neighboring molecules). It is shown that the potential of the first one-electron transfer I1 depends on the level of theory and the model of an environment used in calculations. The potential of the second one-electron transfer I2 depends only on the model of an environment. The analysis of their differences calculated using different approaches has revealed the dependence only from the level of theory. Since DFT methods provide the geometric characteristics of 1,4-dihydroheterocycles closest to the experimental data, it seems reasonable to use these relatively cheap calculations to study the oxidation process.

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1,4-二氢吡啶、1,4-二氢嘧啶和吡咯-1,4-二氢嘧啶的氧化过程:量子化学研究
摘要 1,4-二氢吡啶、1,4-二氢嘧啶及其偶氮类似物的衍生物具有广泛的生物活性,并参与细胞的生物能。由于存在两个单电子转移,二氢环可以被氧化成相应的芳香环。利用不同的理论水平(哈特里-福克、MP2、DFT)、基集和环境模型(真空近似、描述极化环境非特异性影响的 PCM 模型,或描述邻近分子非特异性和特异性影响的带有明确水分子的 PCM 模型),将氧化过程的机理模拟为 1,4-二氢吡啶、1,4-二氢嘧啶和吡咯-1,4-二氢嘧啶的逐步变化。结果表明,第一个单电子转移的电势 I1 取决于理论水平和计算中使用的环境模型。第二个单电子转移的电势 I2 仅取决于环境模型。对使用不同方法计算出的二者差异的分析表明,其依赖性仅来自理论水平。由于 DFT 方法提供的 1,4-二氢杂环的几何特征最接近实验数据,因此使用这些相对便宜的计算方法来研究氧化过程似乎是合理的。
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来源期刊
Structural Chemistry
Structural Chemistry 化学-化学综合
CiteScore
3.80
自引率
11.80%
发文量
227
审稿时长
3.7 months
期刊介绍: Structural Chemistry is an international forum for the publication of peer-reviewed original research papers that cover the condensed and gaseous states of matter and involve numerous techniques for the determination of structure and energetics, their results, and the conclusions derived from these studies. The journal overcomes the unnatural separation in the current literature among the areas of structure determination, energetics, and applications, as well as builds a bridge to other chemical disciplines. Ist comprehensive coverage encompasses broad discussion of results, observation of relationships among various properties, and the description and application of structure and energy information in all domains of chemistry. We welcome the broadest range of accounts of research in structural chemistry involving the discussion of methodologies and structures,experimental, theoretical, and computational, and their combinations. We encourage discussions of structural information collected for their chemicaland biological significance.
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