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
{"title":"Oxidation process of 1,4-dihydropyridine, 1,4-dihydropyrimidine, and pyrrolo-1,4-dihydropyrimidine: quantum chemical study","authors":"Mariia O. Shyshkina,&nbsp;Serhiy M. Desenko","doi":"10.1007/s11224-024-02284-7","DOIUrl":null,"url":null,"abstract":"<div><p>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 <i>I</i><sub>1</sub> depends on the level of theory and the model of an environment used in calculations. The potential of the second one-electron transfer <i>I</i><sub><i>2</i></sub> 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.</p></div>","PeriodicalId":780,"journal":{"name":"Structural Chemistry","volume":"35 3","pages":"993 - 1002"},"PeriodicalIF":2.1000,"publicationDate":"2024-02-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Structural Chemistry","FirstCategoryId":"92","ListUrlMain":"https://link.springer.com/article/10.1007/s11224-024-02284-7","RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q3","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
引用次数: 0

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.

Abstract Image

查看原文
分享 分享
微信好友 朋友圈 QQ好友 复制链接
本刊更多论文
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。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
求助全文
约1分钟内获得全文 去求助
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.
期刊最新文献
Stabilization of cyclo-N6 by insertion into [18]-annulene: a DFT study Theoretical study of novel antipyrine derivatives as promising corrosion inhibitors for mild steel in an acidic environment Density functional theory studies the interaction of neopentane with functionalized porous graphene An analogous Twisted Little Tale on the significance of unusual infrared frequencies Topological relations between crystal structures: a route to predicting inorganic materials
×
引用
GB/T 7714-2015
复制
MLA
复制
APA
复制
导出至
BibTeX EndNote RefMan NoteFirst NoteExpress
×
×
提示
您的信息不完整,为了账户安全,请先补充。
现在去补充
×
提示
您因"违规操作"
具体请查看互助需知
我知道了
×
提示
现在去查看 取消
×
提示
确定
0
微信
客服QQ
Book学术公众号 扫码关注我们
反馈
×
意见反馈
请填写您的意见或建议
请填写您的手机或邮箱
已复制链接
已复制链接
快去分享给好友吧!
我知道了
×
扫码分享
扫码分享
Book学术官方微信
Book学术文献互助
Book学术文献互助群
群 号:481959085
Book学术
文献互助 智能选刊 最新文献 互助须知 联系我们:info@booksci.cn
Book学术提供免费学术资源搜索服务,方便国内外学者检索中英文文献。致力于提供最便捷和优质的服务体验。
Copyright © 2023 Book学术 All rights reserved.
ghs 京公网安备 11010802042870号 京ICP备2023020795号-1