Wei Huang, Kangqiao Wen, Scott T Laughlin, Jorge Escorihuela
{"title":"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。","authors":"Wei Huang, Kangqiao Wen, Scott T Laughlin, Jorge Escorihuela","doi":"10.1039/d4ob01263a","DOIUrl":null,"url":null,"abstract":"<p><p>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 <i>endo</i>-bicyclo[6.1.0]nonyne (<i>endo</i>-BCN) with 2<i>H</i>-pyran-2-one, 2<i>H</i>-thiopyran-2-one, 2<i>H</i>-pyran-2-thione and 2<i>H</i>-thiopyran-2-thione. These 2<i>H</i>-(thio)pyran-2-(thi)ones have displayed different reactivity towards <i>endo</i>-BCN. Density functional theory (DFT) calculations show, in agreement with experiments, that <i>endo</i>-BCN reacts significantly faster with 2<i>H</i>-thiopyran-2-one compared to other 2<i>H</i>-(thio)pyran-2-(thi)one derivatives because of the lower distortion energy. Experimentally determined second-order rate constants for the reaction of a 2<i>H</i>-pyran-2-thione with different strained derivatives, including a 1-methylcyclopropene derivative and several cycloalkynes (<i>exo</i>-BCN, (1<i>R</i>,8<i>S</i>)-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.</p>","PeriodicalId":96,"journal":{"name":"Organic & Biomolecular Chemistry","volume":null,"pages":null},"PeriodicalIF":2.9000,"publicationDate":"2024-09-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Unveiling the reactivity of 2<i>H</i>-(thio)pyran-2-(thi)ones in cycloaddition reactions with strained alkynes through density functional theory studies.\",\"authors\":\"Wei Huang, Kangqiao Wen, Scott T Laughlin, Jorge Escorihuela\",\"doi\":\"10.1039/d4ob01263a\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p><p>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 <i>endo</i>-bicyclo[6.1.0]nonyne (<i>endo</i>-BCN) with 2<i>H</i>-pyran-2-one, 2<i>H</i>-thiopyran-2-one, 2<i>H</i>-pyran-2-thione and 2<i>H</i>-thiopyran-2-thione. These 2<i>H</i>-(thio)pyran-2-(thi)ones have displayed different reactivity towards <i>endo</i>-BCN. Density functional theory (DFT) calculations show, in agreement with experiments, that <i>endo</i>-BCN reacts significantly faster with 2<i>H</i>-thiopyran-2-one compared to other 2<i>H</i>-(thio)pyran-2-(thi)one derivatives because of the lower distortion energy. Experimentally determined second-order rate constants for the reaction of a 2<i>H</i>-pyran-2-thione with different strained derivatives, including a 1-methylcyclopropene derivative and several cycloalkynes (<i>exo</i>-BCN, (1<i>R</i>,8<i>S</i>)-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.</p>\",\"PeriodicalId\":96,\"journal\":{\"name\":\"Organic & Biomolecular Chemistry\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":2.9000,\"publicationDate\":\"2024-09-20\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Organic & Biomolecular Chemistry\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://doi.org/10.1039/d4ob01263a\",\"RegionNum\":3,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"CHEMISTRY, ORGANIC\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Organic & Biomolecular Chemistry","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1039/d4ob01263a","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, ORGANIC","Score":null,"Total":0}
Unveiling the reactivity of 2H-(thio)pyran-2-(thi)ones in cycloaddition reactions with strained alkynes through density functional theory studies.
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.