Unveiling the reactivity of 2H-(thio)pyran-2-(thi)ones in cycloaddition reactions with strained alkynes through density functional theory studies†

IF 2.7 3区 化学 Q1 CHEMISTRY, ORGANIC Organic & Biomolecular Chemistry Pub Date : 2024-09-16 DOI:10.1039/d4ob01263a
Wei Huang , Kangqiao Wen , Scott T. Laughlin , Jorge Escorihuela
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Abstract

Over the past two decades, click chemistry transformations have revolutionized chemical and biological sciences. Among the different strain-promoted cycloadditions, the inverse electron demand Diels–Alder reaction (IEDDA) has been established as a benchmark reaction. We have theoretically investigated the IEDDA reaction of endo-bicyclo[6.1.0]nonyne (endo-BCN) with 2H-pyran-2-one, 2H-thiopyran-2-one, 2H-pyran-2-thione and 2H-thiopyran-2-thione. These 2H-(thio)pyran-2-(thi)ones have displayed different reactivity towards endo-BCN. Density functional theory (DFT) calculations show, in agreement with experiments, that endo-BCN reacts significantly faster with 2H-thiopyran-2-one compared to other 2H-(thio)pyran-2-(thi)one derivatives because of the lower distortion energy. Experimentally determined second-order rate constants for the reaction of a 2H-pyran-2-thione with different strained derivatives, including a 1-methylcyclopropene derivative and several cycloalkynes (exo-BCN, (1R,8S)-bicyclo[6.1.0]non-4-yne-9,9-diyl)dimethanol, dibenzocycylooctyne and a light activatable silacycloheptyne, were used to validate the computational investigations and shed light on this reaction.

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通过密度泛函理论研究揭示 2H-(硫)吡喃-2-(硫)-1 在与受约束炔烃的环加成反应中的反应性。
在过去二十年里,点击化学转化给化学和生物科学带来了革命性的变化。在各种应变促进的环加成反应中,反电子需求 Diels-Alder 反应(IEDDA)已被确立为基准反应。我们从理论上研究了内双环[6.1.0]壬炔(endo-BCN)与 2H-吡喃-2-酮、2H-噻喃-2-酮、2H-吡喃-2-硫酮和 2H-噻喃-2-硫酮的 IEDDA 反应。这些 2H-(硫)吡喃-2-(硫)酮对内生 BCN 的反应活性各不相同。密度泛函理论(DFT)计算显示,内生 BCN 与 2H-噻喃-2-酮的反应速度明显快于其他 2H-(硫代)吡喃-2-(硫)一衍生物,这与实验结果一致,因为后者的畸变能更低。实验测定的 2H-吡喃-2-硫酮与不同应变衍生物(包括 1-甲基环丙烯衍生物和几种环炔烃(exo-BCN、(1R,8S)-双环[6.1.0]壬-4-炔-9,9-二基)二甲醇、二苯并环辛炔和一种可光活化的硅杂环庚炔)反应的二阶速率常数被用来验证计算研究并揭示这一反应。
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来源期刊
Organic & Biomolecular Chemistry
Organic & Biomolecular Chemistry 化学-有机化学
CiteScore
5.50
自引率
9.40%
发文量
1056
审稿时长
1.3 months
期刊介绍: Organic & Biomolecular Chemistry is an international journal using integrated research in chemistry-organic chemistry. Founded in 2003 by the Royal Society of Chemistry, the journal is published in Semimonthly issues and has been indexed by SCIE, a leading international database. The journal focuses on the key research and cutting-edge progress in the field of chemistry-organic chemistry, publishes and reports the research results in this field in a timely manner, and is committed to becoming a window and platform for rapid academic exchanges among peers in this field. The journal's impact factor in 2023 is 2.9, and its CiteScore is 5.5.
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