Hydrothiolation of alkynes with thiol–catechol derivatives catalysed by CuNPs/TiO 2 : exploring the reaction mechanism by DFT calculations

Autores
Capurso, Matias Tomas; Radivoy, Gabriel Eduardo; Nador, Fabiana Gabriela; Dorn, Viviana
Año de publicación
2023
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
Density functional theory (DFT) calculations were applied to describe the hydrothiolation reaction of activated alkynes with thiols bearing a catechol group. The thiol-yne click (TYC) process was efficiently catalysed by a CuNPs/TiO2 nanocatalyst giving the corresponding anti-Markovnikov vinyl sulphides with high Z-stereoselectivity. Based on the experimental results and DFT studies, a plausible reaction mechanism is proposed, which implies the activation of the carbon–carbon triple bond by coordination to the copper centre, followed by a stereoselective (external) nucleophilic attack to give preferentially the Z-vinyl sulphide isomer. Additionally, experimental and theoretical studies strongly correlate with the proposed synergistic role for the TiO2 support in the catalytic process.
Fil: Capurso, Matias Tomas. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Química del Sur. Universidad Nacional del Sur. Departamento de Química. Instituto de Química del Sur; Argentina
Fil: Radivoy, Gabriel Eduardo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Química del Sur. Universidad Nacional del Sur. Departamento de Química. Instituto de Química del Sur; Argentina
Fil: Nador, Fabiana Gabriela. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Química del Sur. Universidad Nacional del Sur. Departamento de Química. Instituto de Química del Sur; Argentina
Fil: Dorn, Viviana. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Química del Sur. Universidad Nacional del Sur. Departamento de Química. Instituto de Química del Sur; Argentina
Materia
DFT METHODS
COPPER NANOCATALYSIS
ALKYNES
HYDROTHIOLATION
Nivel de accesibilidad
acceso abierto
Condiciones de uso
https://creativecommons.org/licenses/by-nc/2.5/ar/
Repositorio
CONICET Digital (CONICET)
Institución
Consejo Nacional de Investigaciones Científicas y Técnicas
OAI Identificador
oai:ri.conicet.gov.ar:11336/249517
Acceder
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network_name_str CONICET Digital (CONICET)
spelling Hydrothiolation of alkynes with thiol–catechol derivatives catalysed by CuNPs/TiO 2 : exploring the reaction mechanism by DFT calculationsCapurso, Matias TomasRadivoy, Gabriel EduardoNador, Fabiana GabrielaDorn, VivianaDFT METHODSCOPPER NANOCATALYSISALKYNESHYDROTHIOLATIONhttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1Density functional theory (DFT) calculations were applied to describe the hydrothiolation reaction of activated alkynes with thiols bearing a catechol group. The thiol-yne click (TYC) process was efficiently catalysed by a CuNPs/TiO2 nanocatalyst giving the corresponding anti-Markovnikov vinyl sulphides with high Z-stereoselectivity. Based on the experimental results and DFT studies, a plausible reaction mechanism is proposed, which implies the activation of the carbon–carbon triple bond by coordination to the copper centre, followed by a stereoselective (external) nucleophilic attack to give preferentially the Z-vinyl sulphide isomer. Additionally, experimental and theoretical studies strongly correlate with the proposed synergistic role for the TiO2 support in the catalytic process.Fil: Capurso, Matias Tomas. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Química del Sur. Universidad Nacional del Sur. Departamento de Química. Instituto de Química del Sur; ArgentinaFil: Radivoy, Gabriel Eduardo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Química del Sur. Universidad Nacional del Sur. Departamento de Química. Instituto de Química del Sur; ArgentinaFil: Nador, Fabiana Gabriela. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Química del Sur. Universidad Nacional del Sur. Departamento de Química. Instituto de Química del Sur; ArgentinaFil: Dorn, Viviana. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Química del Sur. Universidad Nacional del Sur. Departamento de Química. Instituto de Química del Sur; ArgentinaRoyal Society of Chemistry2023-03-10info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfapplication/pdfapplication/pdfapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/249517Capurso, Matias Tomas; Radivoy, Gabriel Eduardo; Nador, Fabiana Gabriela; Dorn, Viviana; Hydrothiolation of alkynes with thiol–catechol derivatives catalysed by CuNPs/TiO 2 : exploring the reaction mechanism by DFT calculations; Royal Society of Chemistry; RSC Advances; 13; 12; 10-3-2023; 8025-80332046-2069CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/https://pubs.rsc.org/en/content/articlelanding/2023/ra/d3ra00169einfo:eu-repo/semantics/altIdentifier/doi/10.1039/D3RA00169Einfo:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-29T09:51:53Zoai:ri.conicet.gov.ar:11336/249517instacron:CONICETInstitucionalhttp://ri.conicet.gov.ar/Organismo científico-tecnológicoNo correspondehttp://ri.conicet.gov.ar/oai/requestdasensio@conicet.gov.ar; lcarlino@conicet.gov.arArgentinaNo correspondeNo correspondeNo correspondeopendoar:34982025-09-29 09:51:54.053CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Hydrothiolation of alkynes with thiol–catechol derivatives catalysed by CuNPs/TiO 2 : exploring the reaction mechanism by DFT calculations
title Hydrothiolation of alkynes with thiol–catechol derivatives catalysed by CuNPs/TiO 2 : exploring the reaction mechanism by DFT calculations
spellingShingle Hydrothiolation of alkynes with thiol–catechol derivatives catalysed by CuNPs/TiO 2 : exploring the reaction mechanism by DFT calculations
Capurso, Matias Tomas
DFT METHODS
COPPER NANOCATALYSIS
ALKYNES
HYDROTHIOLATION
title_short Hydrothiolation of alkynes with thiol–catechol derivatives catalysed by CuNPs/TiO 2 : exploring the reaction mechanism by DFT calculations
title_full Hydrothiolation of alkynes with thiol–catechol derivatives catalysed by CuNPs/TiO 2 : exploring the reaction mechanism by DFT calculations
title_fullStr Hydrothiolation of alkynes with thiol–catechol derivatives catalysed by CuNPs/TiO 2 : exploring the reaction mechanism by DFT calculations
title_full_unstemmed Hydrothiolation of alkynes with thiol–catechol derivatives catalysed by CuNPs/TiO 2 : exploring the reaction mechanism by DFT calculations
title_sort Hydrothiolation of alkynes with thiol–catechol derivatives catalysed by CuNPs/TiO 2 : exploring the reaction mechanism by DFT calculations
dc.creator.none.fl_str_mv Capurso, Matias Tomas
Radivoy, Gabriel Eduardo
Nador, Fabiana Gabriela
Dorn, Viviana
author Capurso, Matias Tomas
author_facet Capurso, Matias Tomas
Radivoy, Gabriel Eduardo
Nador, Fabiana Gabriela
Dorn, Viviana
author_role author
author2 Radivoy, Gabriel Eduardo
Nador, Fabiana Gabriela
Dorn, Viviana
author2_role author
author
author
dc.subject.none.fl_str_mv DFT METHODS
COPPER NANOCATALYSIS
ALKYNES
HYDROTHIOLATION
topic DFT METHODS
COPPER NANOCATALYSIS
ALKYNES
HYDROTHIOLATION
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv Density functional theory (DFT) calculations were applied to describe the hydrothiolation reaction of activated alkynes with thiols bearing a catechol group. The thiol-yne click (TYC) process was efficiently catalysed by a CuNPs/TiO2 nanocatalyst giving the corresponding anti-Markovnikov vinyl sulphides with high Z-stereoselectivity. Based on the experimental results and DFT studies, a plausible reaction mechanism is proposed, which implies the activation of the carbon–carbon triple bond by coordination to the copper centre, followed by a stereoselective (external) nucleophilic attack to give preferentially the Z-vinyl sulphide isomer. Additionally, experimental and theoretical studies strongly correlate with the proposed synergistic role for the TiO2 support in the catalytic process.
Fil: Capurso, Matias Tomas. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Química del Sur. Universidad Nacional del Sur. Departamento de Química. Instituto de Química del Sur; Argentina
Fil: Radivoy, Gabriel Eduardo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Química del Sur. Universidad Nacional del Sur. Departamento de Química. Instituto de Química del Sur; Argentina
Fil: Nador, Fabiana Gabriela. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Química del Sur. Universidad Nacional del Sur. Departamento de Química. Instituto de Química del Sur; Argentina
Fil: Dorn, Viviana. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Química del Sur. Universidad Nacional del Sur. Departamento de Química. Instituto de Química del Sur; Argentina
description Density functional theory (DFT) calculations were applied to describe the hydrothiolation reaction of activated alkynes with thiols bearing a catechol group. The thiol-yne click (TYC) process was efficiently catalysed by a CuNPs/TiO2 nanocatalyst giving the corresponding anti-Markovnikov vinyl sulphides with high Z-stereoselectivity. Based on the experimental results and DFT studies, a plausible reaction mechanism is proposed, which implies the activation of the carbon–carbon triple bond by coordination to the copper centre, followed by a stereoselective (external) nucleophilic attack to give preferentially the Z-vinyl sulphide isomer. Additionally, experimental and theoretical studies strongly correlate with the proposed synergistic role for the TiO2 support in the catalytic process.
publishDate 2023
dc.date.none.fl_str_mv 2023-03-10
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/publishedVersion
http://purl.org/coar/resource_type/c_6501
info:ar-repo/semantics/articulo
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/11336/249517
Capurso, Matias Tomas; Radivoy, Gabriel Eduardo; Nador, Fabiana Gabriela; Dorn, Viviana; Hydrothiolation of alkynes with thiol–catechol derivatives catalysed by CuNPs/TiO 2 : exploring the reaction mechanism by DFT calculations; Royal Society of Chemistry; RSC Advances; 13; 12; 10-3-2023; 8025-8033
2046-2069
CONICET Digital
CONICET
url http://hdl.handle.net/11336/249517
identifier_str_mv Capurso, Matias Tomas; Radivoy, Gabriel Eduardo; Nador, Fabiana Gabriela; Dorn, Viviana; Hydrothiolation of alkynes with thiol–catechol derivatives catalysed by CuNPs/TiO 2 : exploring the reaction mechanism by DFT calculations; Royal Society of Chemistry; RSC Advances; 13; 12; 10-3-2023; 8025-8033
2046-2069
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/url/https://pubs.rsc.org/en/content/articlelanding/2023/ra/d3ra00169e
info:eu-repo/semantics/altIdentifier/doi/10.1039/D3RA00169E
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
https://creativecommons.org/licenses/by-nc/2.5/ar/
eu_rights_str_mv openAccess
rights_invalid_str_mv https://creativecommons.org/licenses/by-nc/2.5/ar/
dc.format.none.fl_str_mv application/pdf
application/pdf
application/pdf
application/pdf
application/pdf
application/pdf
dc.publisher.none.fl_str_mv Royal Society of Chemistry
publisher.none.fl_str_mv Royal Society of Chemistry
dc.source.none.fl_str_mv reponame:CONICET Digital (CONICET)
instname:Consejo Nacional de Investigaciones Científicas y Técnicas
reponame_str CONICET Digital (CONICET)
collection CONICET Digital (CONICET)
instname_str Consejo Nacional de Investigaciones Científicas y Técnicas
repository.name.fl_str_mv CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicas
repository.mail.fl_str_mv dasensio@conicet.gov.ar; lcarlino@conicet.gov.ar
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score 13.070432

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