Explaining the selectivities and the mechanism of [3+2] cycloloaddition reaction between isoalantolactone and diazocyclopropane

• Published in: Journal of molecular modeling 2023-09, Vol.29 (9), p.280-280, Article 280
• Main Authors: Ouled Aitouna, Anas, Barhoumi, Ali, El Alaoui El Abdallaoui, Habib, Mazoir, Noureddine, Elalaoui Belghiti, Mohammed, Syed, Asad, Bahkali, Ali H., Verma, Meenakshi, Zeroual, Abdellah
• Format: Article
• Language: English
• Subjects: Activation energy; Characterization and Evaluation of Materials; Chemistry; Chemistry and Materials Science; Computational chemistry; Computer Appl. in Life Sciences; Computer Applications in Chemistry; Context; Continuum modeling; Cycloaddition; Dichloromethane; Molecular Medicine; Nucleophiles; Optimization; Original Paper; Solvation; Theoretical and Computational Chemistry
• ISSN: 1610-2940; 0948-5023
• DOI: 10.1007/s00894-023-05688-0

Context [3+2] cycloaddition processes between isoalantolactone ( ISALL ) and diazocyclopropane ( DCYP ), have been surveyed exercising the MEDT, reactivity indices, reactions, and activation energies, are computed. In an investigation of conceptual DFT indices, DCYP behaves as a nucleophile in this reaction, whereas ISALL acts as an electrophile. This cyclization is stereo-, chemo-, and regiospecific, as demonstrated by the activation and reaction energies, in clear agreement with the experiment’s results. The mechanism for this [3+2] cycloaddition is occurring in two steps, according to ELF analysis. Methods For the purposes of this investigation, all computations were performed using the Gaussian 09 program. The optimization was completed using Berny’s computational gradient optimization approach with the basis set 6-311G(d,p) and wB97XD functional. Frequency computations were utilized to characterize and locate stationary points where the transition phases have just one imaginary frequency and all frequencies for the reactants and products are positive. After evaluating the effect of dichloromethane (DCM) as a reaction solvent, the stationary point optimization was updated using the polarizable continuum model (PCM) developed by the Tomasi team. The electron localization function (ELF) has been examined within the context of topological investigations using Multiwfn software with a 0.05 grid step. Graphical Abstract