Solvent Effects in the Regioselective N-Functionalization of Tautomerizable Heterocycles Catalyzed by Methyl Trifluoromethanesulfonate: A Density Functional Theory Study with Implicit Solvent Model

Detalhes bibliográficos
Autor(a) principal: Morgon, Nelson H.
Data de Publicação: 2022
Outros Autores: Biswas, Srijit, Duari, Surajit, de Souza, Aguinaldo R. [UNESP]
Tipo de documento: Artigo
Idioma: eng
Título da fonte: Repositório Institucional da UNESP
Texto Completo: http://dx.doi.org/10.3390/computation10100172
http://hdl.handle.net/11449/246157
Resumo: Methyl trifluoromethanesulfonate was found to catalyze the reaction of the nucleophilic substitution of the hydroxyl group of alcohols by N-heterocycles followed by X- to N- alkyl group migration (X = O, S) to obtain N-functionalized benzoxazolone, benzothiazolethione, indoline, benzoimidazolethione and pyridinone derivatives. A high degree of solvent dependency on the yield of the products was observed during optimization of the reaction parameters. The yield of the product was found to be 0%, 48% and 70% in acetonitrile, 1,2-dichloroethane and chloroform, respectively. The mechanism of the reaction was established through experiments as well as DFT calculations. The functional B3LYP and 6-311++G(d) basis function sets were used to optimize the molecular geometries. D3 Grimme empiric dispersion with Becke–Johnson dumping was employed, and harmonic vibrational frequencies were calculated to characterize the stationary points on the potential energy surface. To ensure that all the stationary points were smoothly connected to each other, intrinsic reaction coordinate (IRC) analyses were performed. The influence of solvents was considered using the solvation model based on density (SMD). The free energy profiles of the mechanisms were obtained with vibrational unscaled zero-point vibrational energy (ZPE), thermal, enthalpy, entropic and solvent corrections.
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spelling Solvent Effects in the Regioselective N-Functionalization of Tautomerizable Heterocycles Catalyzed by Methyl Trifluoromethanesulfonate: A Density Functional Theory Study with Implicit Solvent Modeldensity functional theorymethyl trifluoromethanesulfonatepotential energy surfacesolvent effectsMethyl trifluoromethanesulfonate was found to catalyze the reaction of the nucleophilic substitution of the hydroxyl group of alcohols by N-heterocycles followed by X- to N- alkyl group migration (X = O, S) to obtain N-functionalized benzoxazolone, benzothiazolethione, indoline, benzoimidazolethione and pyridinone derivatives. A high degree of solvent dependency on the yield of the products was observed during optimization of the reaction parameters. The yield of the product was found to be 0%, 48% and 70% in acetonitrile, 1,2-dichloroethane and chloroform, respectively. The mechanism of the reaction was established through experiments as well as DFT calculations. The functional B3LYP and 6-311++G(d) basis function sets were used to optimize the molecular geometries. D3 Grimme empiric dispersion with Becke–Johnson dumping was employed, and harmonic vibrational frequencies were calculated to characterize the stationary points on the potential energy surface. To ensure that all the stationary points were smoothly connected to each other, intrinsic reaction coordinate (IRC) analyses were performed. The influence of solvents was considered using the solvation model based on density (SMD). The free energy profiles of the mechanisms were obtained with vibrational unscaled zero-point vibrational energy (ZPE), thermal, enthalpy, entropic and solvent corrections.Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)Department of Physical Chemistry Institute of Chemistry Campinas State UniversityDepartment of Chemistry University of Calcuta, 92, A.P.C. Road, West BengalDepartment of Chemistry School of Science São Paulo State UniversityDepartment of Chemistry School of Science São Paulo State UniversityFAPESP: 15/22338-9FAPESP: 19/12294-5Universidade Estadual de Campinas (UNICAMP)University of CalcutaUniversidade Estadual Paulista (UNESP)Morgon, Nelson H.Biswas, SrijitDuari, Surajitde Souza, Aguinaldo R. [UNESP]2023-07-29T12:33:14Z2023-07-29T12:33:14Z2022-10-01info:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/articlehttp://dx.doi.org/10.3390/computation10100172Computation, v. 10, n. 10, 2022.2079-3197http://hdl.handle.net/11449/24615710.3390/computation101001722-s2.0-85140593807Scopusreponame:Repositório Institucional da UNESPinstname:Universidade Estadual Paulista (UNESP)instacron:UNESPengComputationinfo:eu-repo/semantics/openAccess2023-07-29T12:33:14Zoai:repositorio.unesp.br:11449/246157Repositório InstitucionalPUBhttp://repositorio.unesp.br/oai/requestopendoar:29462024-08-05T18:49:37.245308Repositório Institucional da UNESP - Universidade Estadual Paulista (UNESP)false
dc.title.none.fl_str_mv Solvent Effects in the Regioselective N-Functionalization of Tautomerizable Heterocycles Catalyzed by Methyl Trifluoromethanesulfonate: A Density Functional Theory Study with Implicit Solvent Model
title Solvent Effects in the Regioselective N-Functionalization of Tautomerizable Heterocycles Catalyzed by Methyl Trifluoromethanesulfonate: A Density Functional Theory Study with Implicit Solvent Model
spellingShingle Solvent Effects in the Regioselective N-Functionalization of Tautomerizable Heterocycles Catalyzed by Methyl Trifluoromethanesulfonate: A Density Functional Theory Study with Implicit Solvent Model
Morgon, Nelson H.
density functional theory
methyl trifluoromethanesulfonate
potential energy surface
solvent effects
title_short Solvent Effects in the Regioselective N-Functionalization of Tautomerizable Heterocycles Catalyzed by Methyl Trifluoromethanesulfonate: A Density Functional Theory Study with Implicit Solvent Model
title_full Solvent Effects in the Regioselective N-Functionalization of Tautomerizable Heterocycles Catalyzed by Methyl Trifluoromethanesulfonate: A Density Functional Theory Study with Implicit Solvent Model
title_fullStr Solvent Effects in the Regioselective N-Functionalization of Tautomerizable Heterocycles Catalyzed by Methyl Trifluoromethanesulfonate: A Density Functional Theory Study with Implicit Solvent Model
title_full_unstemmed Solvent Effects in the Regioselective N-Functionalization of Tautomerizable Heterocycles Catalyzed by Methyl Trifluoromethanesulfonate: A Density Functional Theory Study with Implicit Solvent Model
title_sort Solvent Effects in the Regioselective N-Functionalization of Tautomerizable Heterocycles Catalyzed by Methyl Trifluoromethanesulfonate: A Density Functional Theory Study with Implicit Solvent Model
author Morgon, Nelson H.
author_facet Morgon, Nelson H.
Biswas, Srijit
Duari, Surajit
de Souza, Aguinaldo R. [UNESP]
author_role author
author2 Biswas, Srijit
Duari, Surajit
de Souza, Aguinaldo R. [UNESP]
author2_role author
author
author
dc.contributor.none.fl_str_mv Universidade Estadual de Campinas (UNICAMP)
University of Calcuta
Universidade Estadual Paulista (UNESP)
dc.contributor.author.fl_str_mv Morgon, Nelson H.
Biswas, Srijit
Duari, Surajit
de Souza, Aguinaldo R. [UNESP]
dc.subject.por.fl_str_mv density functional theory
methyl trifluoromethanesulfonate
potential energy surface
solvent effects
topic density functional theory
methyl trifluoromethanesulfonate
potential energy surface
solvent effects
description Methyl trifluoromethanesulfonate was found to catalyze the reaction of the nucleophilic substitution of the hydroxyl group of alcohols by N-heterocycles followed by X- to N- alkyl group migration (X = O, S) to obtain N-functionalized benzoxazolone, benzothiazolethione, indoline, benzoimidazolethione and pyridinone derivatives. A high degree of solvent dependency on the yield of the products was observed during optimization of the reaction parameters. The yield of the product was found to be 0%, 48% and 70% in acetonitrile, 1,2-dichloroethane and chloroform, respectively. The mechanism of the reaction was established through experiments as well as DFT calculations. The functional B3LYP and 6-311++G(d) basis function sets were used to optimize the molecular geometries. D3 Grimme empiric dispersion with Becke–Johnson dumping was employed, and harmonic vibrational frequencies were calculated to characterize the stationary points on the potential energy surface. To ensure that all the stationary points were smoothly connected to each other, intrinsic reaction coordinate (IRC) analyses were performed. The influence of solvents was considered using the solvation model based on density (SMD). The free energy profiles of the mechanisms were obtained with vibrational unscaled zero-point vibrational energy (ZPE), thermal, enthalpy, entropic and solvent corrections.
publishDate 2022
dc.date.none.fl_str_mv 2022-10-01
2023-07-29T12:33:14Z
2023-07-29T12:33:14Z
dc.type.status.fl_str_mv info:eu-repo/semantics/publishedVersion
dc.type.driver.fl_str_mv info:eu-repo/semantics/article
format article
status_str publishedVersion
dc.identifier.uri.fl_str_mv http://dx.doi.org/10.3390/computation10100172
Computation, v. 10, n. 10, 2022.
2079-3197
http://hdl.handle.net/11449/246157
10.3390/computation10100172
2-s2.0-85140593807
url http://dx.doi.org/10.3390/computation10100172
http://hdl.handle.net/11449/246157
identifier_str_mv Computation, v. 10, n. 10, 2022.
2079-3197
10.3390/computation10100172
2-s2.0-85140593807
dc.language.iso.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv Computation
dc.rights.driver.fl_str_mv info:eu-repo/semantics/openAccess
eu_rights_str_mv openAccess
dc.source.none.fl_str_mv Scopus
reponame:Repositório Institucional da UNESP
instname:Universidade Estadual Paulista (UNESP)
instacron:UNESP
instname_str Universidade Estadual Paulista (UNESP)
instacron_str UNESP
institution UNESP
reponame_str Repositório Institucional da UNESP
collection Repositório Institucional da UNESP
repository.name.fl_str_mv Repositório Institucional da UNESP - Universidade Estadual Paulista (UNESP)
repository.mail.fl_str_mv
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