Regioselective N-Functionalization of Tautomerizable Heterocycles through Methyl Trifluoromethanesulfonate-Catalyzed Substitution of Alcohols and Alkyl Group Migrations
Autor(a) principal: | |
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Data de Publicação: | 2022 |
Outros Autores: | , , , , , , , |
Tipo de documento: | Artigo |
Idioma: | eng |
Título da fonte: | Repositório Institucional da UNESP |
Texto Completo: | http://dx.doi.org/10.1002/adsc.202101196 http://hdl.handle.net/11449/231595 |
Resumo: | A catalytic synthetic strategy has been developed combining two protocols, such as, direct nucleophilic substitution of alcohols followed by X- to N- alkyl group migration (X=O, S) to access N-functionalized benzoxazolones, benzothiazolethiones, indolinone, benzoimidazolethiones, and pyridinones derivatives. Methyl trifluoromethanesulfonate (MeOTf) was found to catalyze the reaction, which revealed the catalytic property of MeOTf. A mechanism was established through experiments as well as DFT calculations wherein the −OH group of alcohols were converted to the corresponding −OMe groups and in situ generated TfOH. The −OMe groups produced underwent TfOH catalyzed −X alkylation (X=O, S) of the heterocycles followed by −X- to −N-alkyl group migrations in a single step. (Figure presented.). |
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Regioselective N-Functionalization of Tautomerizable Heterocycles through Methyl Trifluoromethanesulfonate-Catalyzed Substitution of Alcohols and Alkyl Group MigrationsAlcoholsAlkylationHeterocyclesMeOTf CatalystNucleophilic SubstitutionRearrangementA catalytic synthetic strategy has been developed combining two protocols, such as, direct nucleophilic substitution of alcohols followed by X- to N- alkyl group migration (X=O, S) to access N-functionalized benzoxazolones, benzothiazolethiones, indolinone, benzoimidazolethiones, and pyridinones derivatives. Methyl trifluoromethanesulfonate (MeOTf) was found to catalyze the reaction, which revealed the catalytic property of MeOTf. A mechanism was established through experiments as well as DFT calculations wherein the −OH group of alcohols were converted to the corresponding −OMe groups and in situ generated TfOH. The −OMe groups produced underwent TfOH catalyzed −X alkylation (X=O, S) of the heterocycles followed by −X- to −N-alkyl group migrations in a single step. (Figure presented.).Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)Department of Chemistry University of Calcutta, 92, A. P. C. Road, West BengalDepartment of Medicinal and Process Chemistry CSIR-Central Drug Research Institute, U. P.Department of Chemistry School of Science São Paulo State University, São PauloDepartment of Chemistry Imam Abdulrahman Bin Faisal University P.O. Box 1982Department of Physical Chemistry Institute of Chemistry Campinas State University, São PauloDepartment of Chemistry School of Science São Paulo State University, São PauloCNPq: 303581/2018-2CNPq: 305541/2017-0University of CalcuttaCSIR-Central Drug Research InstituteUniversidade Estadual Paulista (UNESP)P.O. Box 1982Universidade Estadual de Campinas (UNICAMP)Duari, SurajitBiswas, SubrataRoy, ArnabMaity, SrabaniMishra, Abhishek Kumarde Souza, Aguinaldo R. [UNESP]Elsharif, Asma M.Morgon, Nelson H.Biswas, Srijit2022-04-29T08:46:19Z2022-04-29T08:46:19Z2022-02-15info:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/article865-872http://dx.doi.org/10.1002/adsc.202101196Advanced Synthesis and Catalysis, v. 364, n. 4, p. 865-872, 2022.1615-41691615-4150http://hdl.handle.net/11449/23159510.1002/adsc.2021011962-s2.0-85122894665Scopusreponame:Repositório Institucional da UNESPinstname:Universidade Estadual Paulista (UNESP)instacron:UNESPengAdvanced Synthesis and Catalysisinfo:eu-repo/semantics/openAccess2022-04-29T08:46:19Zoai:repositorio.unesp.br:11449/231595Repositório InstitucionalPUBhttp://repositorio.unesp.br/oai/requestopendoar:29462024-08-05T16:08:04.017266Repositório Institucional da UNESP - Universidade Estadual Paulista (UNESP)false |
dc.title.none.fl_str_mv |
Regioselective N-Functionalization of Tautomerizable Heterocycles through Methyl Trifluoromethanesulfonate-Catalyzed Substitution of Alcohols and Alkyl Group Migrations |
title |
Regioselective N-Functionalization of Tautomerizable Heterocycles through Methyl Trifluoromethanesulfonate-Catalyzed Substitution of Alcohols and Alkyl Group Migrations |
spellingShingle |
Regioselective N-Functionalization of Tautomerizable Heterocycles through Methyl Trifluoromethanesulfonate-Catalyzed Substitution of Alcohols and Alkyl Group Migrations Duari, Surajit Alcohols Alkylation Heterocycles MeOTf Catalyst Nucleophilic Substitution Rearrangement |
title_short |
Regioselective N-Functionalization of Tautomerizable Heterocycles through Methyl Trifluoromethanesulfonate-Catalyzed Substitution of Alcohols and Alkyl Group Migrations |
title_full |
Regioselective N-Functionalization of Tautomerizable Heterocycles through Methyl Trifluoromethanesulfonate-Catalyzed Substitution of Alcohols and Alkyl Group Migrations |
title_fullStr |
Regioselective N-Functionalization of Tautomerizable Heterocycles through Methyl Trifluoromethanesulfonate-Catalyzed Substitution of Alcohols and Alkyl Group Migrations |
title_full_unstemmed |
Regioselective N-Functionalization of Tautomerizable Heterocycles through Methyl Trifluoromethanesulfonate-Catalyzed Substitution of Alcohols and Alkyl Group Migrations |
title_sort |
Regioselective N-Functionalization of Tautomerizable Heterocycles through Methyl Trifluoromethanesulfonate-Catalyzed Substitution of Alcohols and Alkyl Group Migrations |
author |
Duari, Surajit |
author_facet |
Duari, Surajit Biswas, Subrata Roy, Arnab Maity, Srabani Mishra, Abhishek Kumar de Souza, Aguinaldo R. [UNESP] Elsharif, Asma M. Morgon, Nelson H. Biswas, Srijit |
author_role |
author |
author2 |
Biswas, Subrata Roy, Arnab Maity, Srabani Mishra, Abhishek Kumar de Souza, Aguinaldo R. [UNESP] Elsharif, Asma M. Morgon, Nelson H. Biswas, Srijit |
author2_role |
author author author author author author author author |
dc.contributor.none.fl_str_mv |
University of Calcutta CSIR-Central Drug Research Institute Universidade Estadual Paulista (UNESP) P.O. Box 1982 Universidade Estadual de Campinas (UNICAMP) |
dc.contributor.author.fl_str_mv |
Duari, Surajit Biswas, Subrata Roy, Arnab Maity, Srabani Mishra, Abhishek Kumar de Souza, Aguinaldo R. [UNESP] Elsharif, Asma M. Morgon, Nelson H. Biswas, Srijit |
dc.subject.por.fl_str_mv |
Alcohols Alkylation Heterocycles MeOTf Catalyst Nucleophilic Substitution Rearrangement |
topic |
Alcohols Alkylation Heterocycles MeOTf Catalyst Nucleophilic Substitution Rearrangement |
description |
A catalytic synthetic strategy has been developed combining two protocols, such as, direct nucleophilic substitution of alcohols followed by X- to N- alkyl group migration (X=O, S) to access N-functionalized benzoxazolones, benzothiazolethiones, indolinone, benzoimidazolethiones, and pyridinones derivatives. Methyl trifluoromethanesulfonate (MeOTf) was found to catalyze the reaction, which revealed the catalytic property of MeOTf. A mechanism was established through experiments as well as DFT calculations wherein the −OH group of alcohols were converted to the corresponding −OMe groups and in situ generated TfOH. The −OMe groups produced underwent TfOH catalyzed −X alkylation (X=O, S) of the heterocycles followed by −X- to −N-alkyl group migrations in a single step. (Figure presented.). |
publishDate |
2022 |
dc.date.none.fl_str_mv |
2022-04-29T08:46:19Z 2022-04-29T08:46:19Z 2022-02-15 |
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/10.1002/adsc.202101196 Advanced Synthesis and Catalysis, v. 364, n. 4, p. 865-872, 2022. 1615-4169 1615-4150 http://hdl.handle.net/11449/231595 10.1002/adsc.202101196 2-s2.0-85122894665 |
url |
http://dx.doi.org/10.1002/adsc.202101196 http://hdl.handle.net/11449/231595 |
identifier_str_mv |
Advanced Synthesis and Catalysis, v. 364, n. 4, p. 865-872, 2022. 1615-4169 1615-4150 10.1002/adsc.202101196 2-s2.0-85122894665 |
dc.language.iso.fl_str_mv |
eng |
language |
eng |
dc.relation.none.fl_str_mv |
Advanced Synthesis and Catalysis |
dc.rights.driver.fl_str_mv |
info:eu-repo/semantics/openAccess |
eu_rights_str_mv |
openAccess |
dc.format.none.fl_str_mv |
865-872 |
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 |
|
_version_ |
1808128609741701120 |