Modeling of the General Trends of Reactivity and Regioselectivity in Cyclopentadiene–Nitroalkene Diels–Alder Reactions

This study presents a theoretical investigation of the electronic properties of mono- and pentasubstituted cyclopentadiene analogs and variously substituted conjugated nitroalkenes bearing electron-donating and electron-withdrawing groups. Conceptual Density Functional Theory (CDFT) and Electron Loc...

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Main Authors: Adrianna Fałowska, Stanisław Grzybowski, Daniel Kapuściński, Karol Sambora, Agnieszka Łapczuk
Format: Article
Language:English
Published: MDPI AG 2025-06-01
Series:Molecules
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Online Access:https://www.mdpi.com/1420-3049/30/11/2467
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author Adrianna Fałowska
Stanisław Grzybowski
Daniel Kapuściński
Karol Sambora
Agnieszka Łapczuk
author_facet Adrianna Fałowska
Stanisław Grzybowski
Daniel Kapuściński
Karol Sambora
Agnieszka Łapczuk
author_sort Adrianna Fałowska
collection DOAJ
description This study presents a theoretical investigation of the electronic properties of mono- and pentasubstituted cyclopentadiene analogs and variously substituted conjugated nitroalkenes bearing electron-donating and electron-withdrawing groups. Conceptual Density Functional Theory (CDFT) and Electron Localization Function (ELF) analyses were employed to characterize the global and local reactivity indices of the reactants. The obtained data provided insights into the nucleophilic and electrophilic nature of the investigated systems, allowing for the prediction of their reactivity patterns in Diels–Alder reactions. A reactivity model for conjugated alkenes toward cyclopentadienes was developed based on correlation analysis using Hammett substituent constants. This approach enabled the prediction of reaction polarity in (4+2) cycloaddition processes, providing insight into how the electronic effects of substituents influence the reaction course. These findings contribute to a deeper understanding of structure–reactivity relationships in Diels–Alder processes.
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institution Kabale University
issn 1420-3049
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publishDate 2025-06-01
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series Molecules
spelling doaj-art-d6c824e77900437189c42e2c5d1836892025-08-20T03:46:38ZengMDPI AGMolecules1420-30492025-06-013011246710.3390/molecules30112467Modeling of the General Trends of Reactivity and Regioselectivity in Cyclopentadiene–Nitroalkene Diels–Alder ReactionsAdrianna Fałowska0Stanisław Grzybowski1Daniel Kapuściński2Karol Sambora3Agnieszka Łapczuk4Department of Organic Chemistry and Technology, Cracow University of Technology, Warszawska 24, 31-155 Krakow, PolandDepartment of Organic Chemistry and Technology, Cracow University of Technology, Warszawska 24, 31-155 Krakow, PolandDepartment of Organic Chemistry and Technology, Cracow University of Technology, Warszawska 24, 31-155 Krakow, PolandDepartment of Organic Chemistry and Technology, Cracow University of Technology, Warszawska 24, 31-155 Krakow, PolandDepartment of Organic Chemistry and Technology, Cracow University of Technology, Warszawska 24, 31-155 Krakow, PolandThis study presents a theoretical investigation of the electronic properties of mono- and pentasubstituted cyclopentadiene analogs and variously substituted conjugated nitroalkenes bearing electron-donating and electron-withdrawing groups. Conceptual Density Functional Theory (CDFT) and Electron Localization Function (ELF) analyses were employed to characterize the global and local reactivity indices of the reactants. The obtained data provided insights into the nucleophilic and electrophilic nature of the investigated systems, allowing for the prediction of their reactivity patterns in Diels–Alder reactions. A reactivity model for conjugated alkenes toward cyclopentadienes was developed based on correlation analysis using Hammett substituent constants. This approach enabled the prediction of reaction polarity in (4+2) cycloaddition processes, providing insight into how the electronic effects of substituents influence the reaction course. These findings contribute to a deeper understanding of structure–reactivity relationships in Diels–Alder processes.https://www.mdpi.com/1420-3049/30/11/2467reactivity(4+2) cycloadditioncyclic dienesconjugated nitroalkenesCDFTMEDT
spellingShingle Adrianna Fałowska
Stanisław Grzybowski
Daniel Kapuściński
Karol Sambora
Agnieszka Łapczuk
Modeling of the General Trends of Reactivity and Regioselectivity in Cyclopentadiene–Nitroalkene Diels–Alder Reactions
Molecules
reactivity
(4+2) cycloaddition
cyclic dienes
conjugated nitroalkenes
CDFT
MEDT
title Modeling of the General Trends of Reactivity and Regioselectivity in Cyclopentadiene–Nitroalkene Diels–Alder Reactions
title_full Modeling of the General Trends of Reactivity and Regioselectivity in Cyclopentadiene–Nitroalkene Diels–Alder Reactions
title_fullStr Modeling of the General Trends of Reactivity and Regioselectivity in Cyclopentadiene–Nitroalkene Diels–Alder Reactions
title_full_unstemmed Modeling of the General Trends of Reactivity and Regioselectivity in Cyclopentadiene–Nitroalkene Diels–Alder Reactions
title_short Modeling of the General Trends of Reactivity and Regioselectivity in Cyclopentadiene–Nitroalkene Diels–Alder Reactions
title_sort modeling of the general trends of reactivity and regioselectivity in cyclopentadiene nitroalkene diels alder reactions
topic reactivity
(4+2) cycloaddition
cyclic dienes
conjugated nitroalkenes
CDFT
MEDT
url https://www.mdpi.com/1420-3049/30/11/2467
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