Academic Journal
How Bases Catalyze Diels-Alder Reactions
| العنوان: | How Bases Catalyze Diels-Alder Reactions |
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| المؤلفون: | Yu, Song, Tiekink, Eveline H., Vermeeren, Pascal, Bickelhaupt, F. Matthias, Hamlin, Trevor A. |
| المصدر: | Yu , S , Tiekink , E H , Vermeeren , P , Bickelhaupt , F M & Hamlin , T A 2023 , ' How Bases Catalyze Diels-Alder Reactions ' , Chemistry - A European Journal , vol. 29 , no. 7 , e202203121 . https://doi.org/10.1002/chem.202203121 |
| سنة النشر: | 2023 |
| مصطلحات موضوعية: | activation strain model, base catalysis, density functional calculations, Diels-Alder reactions, reactivity, /dk/atira/pure/sustainabledevelopmentgoals/clean_water_and_sanitation, name=SDG 6 - Clean Water and Sanitation |
| الوصف: | We have quantum chemically studied the base-catalyzed Diels-Alder (DA) reaction between 3-hydroxy-2-pyrone and N-methylmaleimide using dispersion-corrected density functional theory. The uncatalyzed reaction is slow and is preceded by the extrusion of CO 2 via a retro-DA reaction. Base catalysis, for example, by triethylamine, lowers the reaction barrier up to 10 kcal mol −1 , causing the reaction to proceed smoothly at low temperature, which quenches the expulsion of CO 2 , yielding efficient access to polyoxygenated natural compounds. Our activation strain analyses reveal that the base accelerates the DA reaction via two distinct electronic mechanisms: i) by the HOMO-raising effect, which enhances the normal electron demand orbital interaction; and ii) by donating charge into 3-hydroxy-2-pyrone which accumulates in its reactive region and promotes strongly stabilizing secondary electrostatic interactions with N-methylmaleimide. |
| نوع الوثيقة: | article in journal/newspaper |
| اللغة: | English |
| DOI: | 10.1002/chem.202203121 |
| الاتاحة: | https://research.vu.nl/en/publications/2eae2f4b-509d-4caa-9563-cb2d6f1d95b1 https://doi.org/10.1002/chem.202203121 https://hdl.handle.net/1871.1/2eae2f4b-509d-4caa-9563-cb2d6f1d95b1 http://www.scopus.com/inward/record.url?scp=85143843312&partnerID=8YFLogxK http://www.scopus.com/inward/citedby.url?scp=85143843312&partnerID=8YFLogxK |
| Rights: | info:eu-repo/semantics/openAccess |
| رقم الانضمام: | edsbas.59723647 |
| قاعدة البيانات: | BASE |
| DOI: | 10.1002/chem.202203121 |
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