A molecular electron density theory study of hydrogen bond catalysed polar Diels–Alder reactions of α,β-unsaturated carbonyl compounds

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dc.contributor.authorDomingo, L.
dc.contributor.authorPérez, P.
dc.contributor.authorRíos-Gutiérrez, M.
dc.contributor.authorAurell, M.
dc.date.accessioned2024-09-10T18:09:51Z
dc.date.available2024-09-10T18:09:51Z
dc.date.issued2024-06
dc.descriptionTEXTO COMPLETO EN INGLÉS
dc.description.abstractThe hydrogen bond (HB) catalysed Diels-Alder (DA) reactions of acrolein with cyclopentadiene have been investigated within the Molecular Electron Density Theory (MEDT) at the ωB97X-D/6-311G(d,p) computational level. The formation of HBs increases the electrophilicity of these species, suggesting an acceleration of these polar Diels-Alder (P-DA) reactions with forward electron density flux. Formation of one or two HBs with acrolein decreases the activation energies of the HB-catalysed P-DA reactions by 1.7 (methanol) and 4.0 (squaramide) kcal·mol−1, with the corresponding DA reactions exhibiting low endo stereoselectivity. These HB-catalysed DA reactions proceed through non-concerted one-step mechanisms via asynchronous transition state structures (TSs). An Interacting Quantum Atoms (IQA) energy partitioning analysis of the TSs indicates that the intra-atomic stabilization of the acrolein framework, coupled with the increase of the global electron density transfer, plays a crucial role in reducing the activation energies of these HB-catalysed DA reactions.
dc.description.urihttps://www-sciencedirect-com.recursosbiblioteca.unab.cl/science/article/pii/S2666951X24000032
dc.identifier.citationTetrahedron Chem, Volume 10 , June 2024, 100064
dc.identifier.doihttps://doi.org/10.1016/j.tchem.2024.100064
dc.identifier.issn2666-951X
dc.identifier.urihttps://repositorio.unab.cl/handle/ria/60036
dc.language.isoen
dc.publisherElsevier
dc.rights.licenseAttribution-NonCommercial-NoDerivatives 4.0 International
dc.subjectDiels-Alder reactions
dc.subjectHydrogen bonds
dc.subjectCatalysis
dc.subjectStereoselectivity
dc.subjectMolecular electron density theory
dc.titleA molecular electron density theory study of hydrogen bond catalysed polar Diels–Alder reactions of α,β-unsaturated carbonyl compounds
dc.typeArtículo
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