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RESEARCH PRODUCT

Unveiling the Different Chemical Reactivity of Diphenyl Nitrilimine and Phenyl Nitrile Oxide in [3+2] Cycloaddition Reactions with (R)-Carvone through the Molecular Electron Density Theory

Mar Ríos-gutiérrezLuis R. DomingoAli OubellaM. EsseffarMy Youssef Ait Itto

subject

Models MolecularNitrilemolecular mechanismsPharmaceutical Science010402 general chemistrynitrilimines01 natural sciencesArticleAnalytical Chemistrylcsh:QD241-441chemistry.chemical_compoundlcsh:Organic chemistryComputational chemistryDrug DiscoveryNitrilesSingle bondReactivity (chemistry)Physical and Theoretical ChemistryChemoselectivityCarbenoidCycloaddition ReactionMolecular Structure010405 organic chemistryChemistryNitrilimineOrganic ChemistryBiphenyl Compoundsmolecular electron density theory[3+2] cycloadditionsCycloaddition0104 chemical sciencesChemistry (miscellaneous)chemoselectivitynitrile oxidesMolecular MedicineQuantum TheoryDensity functional theory

description

The [3+2] cycloaddition (32CA) reactions of diphenyl nitrilimine and phenyl nitrile oxide with (R)-carvone have been studied within the Molecular Electron Density Theory (MEDT). Electron localisation function (ELF) analysis of these three-atom-components (TACs) permits its characterisation as carbenoid and zwitterionic TACs, thus having a different reactivity. The analysis of the conceptual Density Functional Theory (DFT) indices accounts for the very low polar character of these 32CA reactions, while analysis of the DFT energies accounts for the opposite chemoselectivity experimentally observed. Topological analysis of the ELF along the single bond formation makes it possible to characterise the mechanisms of these 32CA reactions as cb- and zw-type. The present MEDT study supports the proposed classification of 32CA reactions into pdr-, pmr-, cb- and zw-type, thus asserting MEDT as the theory able to explain chemical reactivity in Organic Chemistry.

yearjournalcountryeditionlanguage
2020-02-01Molecules
10.3390/molecules25051085http://dx.doi.org/10.3390/molecules25051085