Dienophilic reactivity of 2-phosphaindolizines: a conceptual DFT investigation
The >C=P– or –N=P– functionality in 1,3-azaphospholo[1,5-a]pyridine, named as 2-phosphaindolizine and its 1- and 3-aza derivatives act as dienophiles and undergo Diels–Alder reactions with 1,3-dienes. However, the dienophilic reactivity is affected by the nature of the substituent groups on the t...
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| Format: | Article |
| Language: | English |
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Beilstein-Institut
2022-09-01
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| Series: | Beilstein Journal of Organic Chemistry |
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| Online Access: | https://doi.org/10.3762/bjoc.18.127 |
| _version_ | 1798035609681395712 |
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| author | Nosheen Beig Aarti Peswani Raj Kumar Bansal |
| author_facet | Nosheen Beig Aarti Peswani Raj Kumar Bansal |
| author_sort | Nosheen Beig |
| collection | DOAJ |
| description | The >C=P– or –N=P– functionality in 1,3-azaphospholo[1,5-a]pyridine, named as 2-phosphaindolizine and its 1- and 3-aza derivatives act as dienophiles and undergo Diels–Alder reactions with 1,3-dienes. However, the dienophilic reactivity is affected by the nature of the substituent groups on the two sides of the σ2,λ3-P atom and also by the presence of more nitrogen atom(s) in the five-membered ring. The conceptual density functional theory (DFT) calculations have been used in recent years to predict the reactivity of organic molecules in reactions. We calculated global hardness (η), global softness (S), electronic chemical potential (μ), electrophilicity (ω), and nucleophilicity (N) indices of four classes of 2-phosphaindolizines, on the basis of which their observed relative dienophilic reactivities could be rationalized. Besides, the Fukui functions of the carbon/nitrogen and phosphorus atoms of the >C=P– and –N=P– functionalities were also computed which revealed their hard electrophilic character and accorded well with the dienophilic reactivities observed experimentally. Furthermore, energies and symmetries of the lowest unoccupied molecular orbitals (LUMO) of 2-phosphaindolizines were found to be in conformity with their dienophilic reactivities. |
| first_indexed | 2024-04-11T21:00:35Z |
| format | Article |
| id | doaj.art-e4b0c8aa3ae648cd8db3d55854b6ddbd |
| institution | Directory Open Access Journal |
| issn | 1860-5397 |
| language | English |
| last_indexed | 2024-04-11T21:00:35Z |
| publishDate | 2022-09-01 |
| publisher | Beilstein-Institut |
| record_format | Article |
| series | Beilstein Journal of Organic Chemistry |
| spelling | doaj.art-e4b0c8aa3ae648cd8db3d55854b6ddbd2022-12-22T04:03:32ZengBeilstein-InstitutBeilstein Journal of Organic Chemistry1860-53972022-09-011811217122410.3762/bjoc.18.1271860-5397-18-127Dienophilic reactivity of 2-phosphaindolizines: a conceptual DFT investigationNosheen Beig0Aarti Peswani1Raj Kumar Bansal2Department of Chemistry, The IIS (Deemed to be University), Jaipur 302020, India Department of Chemistry, The IIS (Deemed to be University), Jaipur 302020, India Department of Chemistry, The IIS (Deemed to be University), Jaipur 302020, India The >C=P– or –N=P– functionality in 1,3-azaphospholo[1,5-a]pyridine, named as 2-phosphaindolizine and its 1- and 3-aza derivatives act as dienophiles and undergo Diels–Alder reactions with 1,3-dienes. However, the dienophilic reactivity is affected by the nature of the substituent groups on the two sides of the σ2,λ3-P atom and also by the presence of more nitrogen atom(s) in the five-membered ring. The conceptual density functional theory (DFT) calculations have been used in recent years to predict the reactivity of organic molecules in reactions. We calculated global hardness (η), global softness (S), electronic chemical potential (μ), electrophilicity (ω), and nucleophilicity (N) indices of four classes of 2-phosphaindolizines, on the basis of which their observed relative dienophilic reactivities could be rationalized. Besides, the Fukui functions of the carbon/nitrogen and phosphorus atoms of the >C=P– and –N=P– functionalities were also computed which revealed their hard electrophilic character and accorded well with the dienophilic reactivities observed experimentally. Furthermore, energies and symmetries of the lowest unoccupied molecular orbitals (LUMO) of 2-phosphaindolizines were found to be in conformity with their dienophilic reactivities.https://doi.org/10.3762/bjoc.18.127dienophilic reactivityelectronic chemical potentialelectrophilicity indexfukui functionglobal hardnessnucleophilicity index2-phosphaindolizines |
| spellingShingle | Nosheen Beig Aarti Peswani Raj Kumar Bansal Dienophilic reactivity of 2-phosphaindolizines: a conceptual DFT investigation Beilstein Journal of Organic Chemistry dienophilic reactivity electronic chemical potential electrophilicity index fukui function global hardness nucleophilicity index 2-phosphaindolizines |
| title | Dienophilic reactivity of 2-phosphaindolizines: a conceptual DFT investigation |
| title_full | Dienophilic reactivity of 2-phosphaindolizines: a conceptual DFT investigation |
| title_fullStr | Dienophilic reactivity of 2-phosphaindolizines: a conceptual DFT investigation |
| title_full_unstemmed | Dienophilic reactivity of 2-phosphaindolizines: a conceptual DFT investigation |
| title_short | Dienophilic reactivity of 2-phosphaindolizines: a conceptual DFT investigation |
| title_sort | dienophilic reactivity of 2 phosphaindolizines a conceptual dft investigation |
| topic | dienophilic reactivity electronic chemical potential electrophilicity index fukui function global hardness nucleophilicity index 2-phosphaindolizines |
| url | https://doi.org/10.3762/bjoc.18.127 |
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