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Meta-Hybrid Density Functional Theory Prediction of the Reactivity, Stability, and IGM of Azepane, Oxepane, Thiepane, and Halogenated Cycloheptane
[Image: see text] The application of plain cycloalkanes and heterocyclic derivatives in the synthesis of valuable natural products and pharmacologically active intermediates has increased tremendously in recent times with much attention being paid to the lower cycloalkane members. The structural and...
Autores principales: | , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
American Chemical Society
2022
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Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9088921/ https://www.ncbi.nlm.nih.gov/pubmed/35559178 http://dx.doi.org/10.1021/acsomega.1c07361 |
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author | Unimuke, Tomsmith O. Louis, Hitler Eno, Ededet A. Agwamba, Ernest C. Adeyinka, Adedapo S. |
author_facet | Unimuke, Tomsmith O. Louis, Hitler Eno, Ededet A. Agwamba, Ernest C. Adeyinka, Adedapo S. |
author_sort | Unimuke, Tomsmith O. |
collection | PubMed |
description | [Image: see text] The application of plain cycloalkanes and heterocyclic derivatives in the synthesis of valuable natural products and pharmacologically active intermediates has increased tremendously in recent times with much attention being paid to the lower cycloalkane members. The structural and molecular properties of higher seven-membered and nonaromatic heterocyclic derivatives are less known despite their stable nature and vast application; thus, an insight into their structural and electronic properties is still needed. Appropriate quantum chemical calculations utilizing the ab initio (MP2) method, meta-hybrid (M06-2X) functional, and long-range-separated functionals (ωB97XD) have been utilized in this work to investigate the structural reactivity, stability, and behavior of substituents on cycloheptane (CHP) and its derivatives: azepane, oxepane, thiepane, fluorocycloheptane (FCHP), bromocycloheptane (BrCHP), and chlorocycloheptane (ClCHP). Molecular global reactivity descriptors such as Fukui function, frontier molecular orbitals (FMOs), and molecular electrostatic potential were computed and compared with lower members. The results of two population methods CHELPG and Atomic Dipole Corrected Hirshfeld Charges (ADCH) were equally compared to scrutinize the charge distribution in the molecules. The susceptibility of intramolecular interactions between the substituents and cycloalkane ring is revealed by natural bond orbital analysis and intramolecular weak interactions by the independent gradient model (IGM). Other properties such as atomic density of states, intrinsic bond strength index (IBSI), and dipole moments are considered. It is acclaimed that the strain effect is a major determinant effect in the energy balance of cyclic molecules; thus, the ring strain energies and validation of spectroscopic specificities with reference to the X-ray crystallographic data are also considered. |
format | Online Article Text |
id | pubmed-9088921 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2022 |
publisher | American Chemical Society |
record_format | MEDLINE/PubMed |
spelling | pubmed-90889212022-05-11 Meta-Hybrid Density Functional Theory Prediction of the Reactivity, Stability, and IGM of Azepane, Oxepane, Thiepane, and Halogenated Cycloheptane Unimuke, Tomsmith O. Louis, Hitler Eno, Ededet A. Agwamba, Ernest C. Adeyinka, Adedapo S. ACS Omega [Image: see text] The application of plain cycloalkanes and heterocyclic derivatives in the synthesis of valuable natural products and pharmacologically active intermediates has increased tremendously in recent times with much attention being paid to the lower cycloalkane members. The structural and molecular properties of higher seven-membered and nonaromatic heterocyclic derivatives are less known despite their stable nature and vast application; thus, an insight into their structural and electronic properties is still needed. Appropriate quantum chemical calculations utilizing the ab initio (MP2) method, meta-hybrid (M06-2X) functional, and long-range-separated functionals (ωB97XD) have been utilized in this work to investigate the structural reactivity, stability, and behavior of substituents on cycloheptane (CHP) and its derivatives: azepane, oxepane, thiepane, fluorocycloheptane (FCHP), bromocycloheptane (BrCHP), and chlorocycloheptane (ClCHP). Molecular global reactivity descriptors such as Fukui function, frontier molecular orbitals (FMOs), and molecular electrostatic potential were computed and compared with lower members. The results of two population methods CHELPG and Atomic Dipole Corrected Hirshfeld Charges (ADCH) were equally compared to scrutinize the charge distribution in the molecules. The susceptibility of intramolecular interactions between the substituents and cycloalkane ring is revealed by natural bond orbital analysis and intramolecular weak interactions by the independent gradient model (IGM). Other properties such as atomic density of states, intrinsic bond strength index (IBSI), and dipole moments are considered. It is acclaimed that the strain effect is a major determinant effect in the energy balance of cyclic molecules; thus, the ring strain energies and validation of spectroscopic specificities with reference to the X-ray crystallographic data are also considered. American Chemical Society 2022-04-15 /pmc/articles/PMC9088921/ /pubmed/35559178 http://dx.doi.org/10.1021/acsomega.1c07361 Text en © 2022 The Authors. Published by American Chemical Society https://creativecommons.org/licenses/by-nc-nd/4.0/Permits non-commercial access and re-use, provided that author attribution and integrity are maintained; but does not permit creation of adaptations or other derivative works (https://creativecommons.org/licenses/by-nc-nd/4.0/). |
spellingShingle | Unimuke, Tomsmith O. Louis, Hitler Eno, Ededet A. Agwamba, Ernest C. Adeyinka, Adedapo S. Meta-Hybrid Density Functional Theory Prediction of the Reactivity, Stability, and IGM of Azepane, Oxepane, Thiepane, and Halogenated Cycloheptane |
title | Meta-Hybrid Density Functional Theory Prediction of
the Reactivity, Stability, and IGM of Azepane, Oxepane, Thiepane,
and Halogenated Cycloheptane |
title_full | Meta-Hybrid Density Functional Theory Prediction of
the Reactivity, Stability, and IGM of Azepane, Oxepane, Thiepane,
and Halogenated Cycloheptane |
title_fullStr | Meta-Hybrid Density Functional Theory Prediction of
the Reactivity, Stability, and IGM of Azepane, Oxepane, Thiepane,
and Halogenated Cycloheptane |
title_full_unstemmed | Meta-Hybrid Density Functional Theory Prediction of
the Reactivity, Stability, and IGM of Azepane, Oxepane, Thiepane,
and Halogenated Cycloheptane |
title_short | Meta-Hybrid Density Functional Theory Prediction of
the Reactivity, Stability, and IGM of Azepane, Oxepane, Thiepane,
and Halogenated Cycloheptane |
title_sort | meta-hybrid density functional theory prediction of
the reactivity, stability, and igm of azepane, oxepane, thiepane,
and halogenated cycloheptane |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9088921/ https://www.ncbi.nlm.nih.gov/pubmed/35559178 http://dx.doi.org/10.1021/acsomega.1c07361 |
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