Exploration of the mechanism, chemospecificity, regiospecificity and stereoselectivity of the cycloaddition reaction between 9α-hydroxyparthenolide and nitrilimine: MEDT study

The 32CA cycloaddition reactions of the hydroxyparthenolide with nitrilimine have been studied using molecular electron density theory. The reactivity indices, activation and reaction energies are calculated at the B3LYP/6-31(d) level. The presence of two double bonds in hydroxyparthenolide gives si...

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Bibliographic Details
Published in:Theoretical chemistry accounts 2022-10, Vol.141 (10), Article 50
Main Authors: Ouahdi, Zenab, Ourhriss, Najia, Aitouna, Anas Ouald, Barhoumi, Ali, Belghiti, Mohammed Elalaoui, Moubarik, Amine, El Alaoui El Abdallaoui, Habib, El Idrissi, Mohammed, Zeroual, Abdellah
Format: Article
Language:English
Subjects:
Activation energy
Atomic/Molecular Structure and Spectra
Chemistry
Chemistry and Materials Science
Cycloaddition
Electron density
Inorganic Chemistry
Mathematical analysis
Organic Chemistry
Physical Chemistry
Regular Article
Stereoselectivity
Theoretical and Computational Chemistry
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Summary:The 32CA cycloaddition reactions of the hydroxyparthenolide with nitrilimine have been studied using molecular electron density theory. The reactivity indices, activation and reaction energies are calculated at the B3LYP/6-31(d) level. The presence of two double bonds in hydroxyparthenolide gives six reaction pathways for this cycloaddition. The reaction proceeds via a one-step asynchronous mechanism with a nonpolar character, and an analysis of conceptual DFT indices explains the nonpolar character of this cycloaddition reaction. The calculations of the activation and reaction energies show that this cyclization reaction takes place on the C 1 =C 2 double bond, which indicates that this cycloaddition reaction is chemospecific and regiospecific in full conformity with the experimental results. The reorganization of electrons along the most preferred pathway of the 32CA cycloaddition reaction between hydroxyparthenolide and nitrilimine was investigated using topological analysis of the electron localization function (ELF). ELF analysis revealed that this reaction proceeds through a two-stage one-step mechanism.
ISSN:1432-881X
1432-2234
DOI:10.1007/s00214-022-02913-6