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
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 carben...
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MDPI AG
2020-02-01
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| Series: | Molecules |
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| Online Access: | https://www.mdpi.com/1420-3049/25/5/1085 |
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| author | Mar Ríos-Gutiérrez Luis R. Domingo M’hamed Esseffar Ali Oubella My Youssef Ait Itto |
| author_facet | Mar Ríos-Gutiérrez Luis R. Domingo M’hamed Esseffar Ali Oubella My Youssef Ait Itto |
| author_sort | Mar Ríos-Gutiérrez |
| collection | DOAJ |
| 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 <i>cb-</i> and <i>zw-type.</i> The present MEDT study supports the proposed classification of 32CA reactions into <i>pdr-</i>, <i>pmr-</i>, <i>cb-</i> and <i>zw-type</i>, thus asserting MEDT as the theory able to explain chemical reactivity in Organic Chemistry. |
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| institution | Directory Open Access Journal |
| issn | 1420-3049 |
| language | English |
| last_indexed | 2024-12-20T06:24:03Z |
| publishDate | 2020-02-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Molecules |
| spelling | doaj.art-78507bbdfa1b48c882e9081c28bc6e932022-12-21T19:50:21ZengMDPI AGMolecules1420-30492020-02-01255108510.3390/molecules25051085molecules25051085Unveiling the Different Chemical Reactivity of Diphenyl Nitrilimine and Phenyl Nitrile Oxide in [3+2] Cycloaddition Reactions with (R)-Carvone through the Molecular Electron Density TheoryMar Ríos-Gutiérrez0Luis R. Domingo1M’hamed Esseffar2Ali Oubella3My Youssef Ait Itto4Department of Organic Chemistry, University of Valencia, Dr. Moliner 50, Burjassot, E-46100 Valencia, SpainDepartment of Organic Chemistry, University of Valencia, Dr. Moliner 50, Burjassot, E-46100 Valencia, SpainLaboratoire de Synthèse Organique et Physico-Chimie Moléculaire, Département de Chimie, Faculté des Sciences, Semlalia, B.P 2390, Marrakech 40001, MoroccoLaboratoire de Synthèse Organique et Physico-Chimie Moléculaire, Département de Chimie, Faculté des Sciences, Semlalia, B.P 2390, Marrakech 40001, MoroccoLaboratoire de Synthèse Organique et Physico-Chimie Moléculaire, Département de Chimie, Faculté des Sciences, Semlalia, B.P 2390, Marrakech 40001, MoroccoThe [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 <i>cb-</i> and <i>zw-type.</i> The present MEDT study supports the proposed classification of 32CA reactions into <i>pdr-</i>, <i>pmr-</i>, <i>cb-</i> and <i>zw-type</i>, thus asserting MEDT as the theory able to explain chemical reactivity in Organic Chemistry.https://www.mdpi.com/1420-3049/25/5/1085[3+2] cycloadditionsnitriliminesnitrile oxideschemoselectivitymolecular electron density theorymolecular mechanisms |
| spellingShingle | Mar Ríos-Gutiérrez Luis R. Domingo M’hamed Esseffar Ali Oubella My Youssef Ait Itto 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 Molecules [3+2] cycloadditions nitrilimines nitrile oxides chemoselectivity molecular electron density theory molecular mechanisms |
| title | 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 |
| title_full | 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 |
| title_fullStr | 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 |
| title_full_unstemmed | 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 |
| title_short | 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 |
| title_sort | 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 |
| topic | [3+2] cycloadditions nitrilimines nitrile oxides chemoselectivity molecular electron density theory molecular mechanisms |
| url | https://www.mdpi.com/1420-3049/25/5/1085 |
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