Cross-Dehydrogenative Coupling of Tertiary Amines and Terminal Alkynes Catalyzed by Copper Nanoparticles on Zeolite

Autores
Alonso, Francisco; Arroyo, Adrian; Martín-García, Iris; Moglie, Yanina Fernanda
Año de publicación
2015
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
A wide range of catalysts based on supported copper nanoparticles have been prepared and tested in the cross-dehydrogenative coupling of tertiary amines and terminal alkynes. Copper nanoparticles on zeolite Y were found to be the most effective catalyst in the presence of tert-butyl hydroperoxide as the oxidant. Contrary to the previously reported methodologies involving copper catalysts, reactions have been accomplished without the need of an inert atmosphere and in the absence of solvent, using 1.5 mol% catalyst. A variety of tertiary amines, including aromatic, benzylic and aliphatic ones, have been coupled with both aromatic and aliphatic alkynes to furnish the corresponding propargylamines in moderate-to-excellent yields. The procedure has been successfully scaled-up to 12 mmol with a high conversion (93%). Moreover, the catalyst has been reused in seven cycles maintaining a good performance. Its catalytic activity has been compared with that of an array of commercial copper catalysts, being superior as regards the conversion and minimizing the alkyne homocoupling as a side reaction. The negative filtration test points to a heterogeneous nature of the process. Based on compelling experimental evidence, a novel reaction mechanism has been delineated which outlines the essential role of free radicals and the couple copper(I)/copper(II).
Fil: Alonso, Francisco. Universidad de Alicante. Facultad de Ciencias; España
Fil: Arroyo, Adrian. Universidad de Alicante. Facultad de Ciencias; España
Fil: Martín-García, Iris. Universidad de Alicante. Facultad de Ciencias; España
Fil: Moglie, Yanina Fernanda. Universidad Nacional del Sur. Departamento de Química; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Bahía Blanca. Instituto de Química del Sur; Argentina
Materia
Cross Dehydrogenative Coupling
Heterogeneous Catalysis
Copper Nanoparticles
Zeolites
Alkynes
Amines
Copper
Nivel de accesibilidad
acceso abierto
Condiciones de uso
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
Repositorio
CONICET Digital (CONICET)
Institución
Consejo Nacional de Investigaciones Científicas y Técnicas
OAI Identificador
oai:ri.conicet.gov.ar:11336/4719
Acceder
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network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Cross-Dehydrogenative Coupling of Tertiary Amines and Terminal Alkynes Catalyzed by Copper Nanoparticles on ZeoliteAlonso, Francisco Arroyo, AdrianMartín-García, IrisMoglie, Yanina FernandaCross Dehydrogenative CouplingHeterogeneous CatalysisCopper NanoparticlesZeolitesAlkynesAminesCopperhttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1A wide range of catalysts based on supported copper nanoparticles have been prepared and tested in the cross-dehydrogenative coupling of tertiary amines and terminal alkynes. Copper nanoparticles on zeolite Y were found to be the most effective catalyst in the presence of tert-butyl hydroperoxide as the oxidant. Contrary to the previously reported methodologies involving copper catalysts, reactions have been accomplished without the need of an inert atmosphere and in the absence of solvent, using 1.5 mol% catalyst. A variety of tertiary amines, including aromatic, benzylic and aliphatic ones, have been coupled with both aromatic and aliphatic alkynes to furnish the corresponding propargylamines in moderate-to-excellent yields. The procedure has been successfully scaled-up to 12 mmol with a high conversion (93%). Moreover, the catalyst has been reused in seven cycles maintaining a good performance. Its catalytic activity has been compared with that of an array of commercial copper catalysts, being superior as regards the conversion and minimizing the alkyne homocoupling as a side reaction. The negative filtration test points to a heterogeneous nature of the process. Based on compelling experimental evidence, a novel reaction mechanism has been delineated which outlines the essential role of free radicals and the couple copper(I)/copper(II).Fil: Alonso, Francisco. Universidad de Alicante. Facultad de Ciencias; EspañaFil: Arroyo, Adrian. Universidad de Alicante. Facultad de Ciencias; EspañaFil: Martín-García, Iris. Universidad de Alicante. Facultad de Ciencias; EspañaFil: Moglie, Yanina Fernanda. Universidad Nacional del Sur. Departamento de Química; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Bahía Blanca. Instituto de Química del Sur; ArgentinaWiley2015-10info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/4719Alonso, Francisco; Arroyo, Adrian; Martín-García, Iris; Moglie, Yanina Fernanda; Cross-Dehydrogenative Coupling of Tertiary Amines and Terminal Alkynes Catalyzed by Copper Nanoparticles on Zeolite; Wiley; Advanced Synthesis & Catalysis (print); 357; 16-17; 10-2015; 3549-35611615-4150enginfo:eu-repo/semantics/altIdentifier/url/http://onlinelibrary.wiley.com/doi/10.1002/adsc.201500787/abstractinfo:eu-repo/semantics/altIdentifier/doi/10.1002/adsc.201500787info:eu-repo/semantics/altIdentifier/issn/1615-4150info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-03T09:59:11Zoai:ri.conicet.gov.ar:11336/4719instacron: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:34982025-09-03 09:59:11.986CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Cross-Dehydrogenative Coupling of Tertiary Amines and Terminal Alkynes Catalyzed by Copper Nanoparticles on Zeolite
title Cross-Dehydrogenative Coupling of Tertiary Amines and Terminal Alkynes Catalyzed by Copper Nanoparticles on Zeolite
spellingShingle Cross-Dehydrogenative Coupling of Tertiary Amines and Terminal Alkynes Catalyzed by Copper Nanoparticles on Zeolite
Alonso, Francisco
Cross Dehydrogenative Coupling
Heterogeneous Catalysis
Copper Nanoparticles
Zeolites
Alkynes
Amines
Copper
title_short Cross-Dehydrogenative Coupling of Tertiary Amines and Terminal Alkynes Catalyzed by Copper Nanoparticles on Zeolite
title_full Cross-Dehydrogenative Coupling of Tertiary Amines and Terminal Alkynes Catalyzed by Copper Nanoparticles on Zeolite
title_fullStr Cross-Dehydrogenative Coupling of Tertiary Amines and Terminal Alkynes Catalyzed by Copper Nanoparticles on Zeolite
title_full_unstemmed Cross-Dehydrogenative Coupling of Tertiary Amines and Terminal Alkynes Catalyzed by Copper Nanoparticles on Zeolite
title_sort Cross-Dehydrogenative Coupling of Tertiary Amines and Terminal Alkynes Catalyzed by Copper Nanoparticles on Zeolite
dc.creator.none.fl_str_mv Alonso, Francisco
Arroyo, Adrian
Martín-García, Iris
Moglie, Yanina Fernanda
author Alonso, Francisco
author_facet Alonso, Francisco
Arroyo, Adrian
Martín-García, Iris
Moglie, Yanina Fernanda
author_role author
author2 Arroyo, Adrian
Martín-García, Iris
Moglie, Yanina Fernanda
author2_role author
author
author
dc.subject.none.fl_str_mv Cross Dehydrogenative Coupling
Heterogeneous Catalysis
Copper Nanoparticles
Zeolites
Alkynes
Amines
Copper
topic Cross Dehydrogenative Coupling
Heterogeneous Catalysis
Copper Nanoparticles
Zeolites
Alkynes
Amines
Copper
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv A wide range of catalysts based on supported copper nanoparticles have been prepared and tested in the cross-dehydrogenative coupling of tertiary amines and terminal alkynes. Copper nanoparticles on zeolite Y were found to be the most effective catalyst in the presence of tert-butyl hydroperoxide as the oxidant. Contrary to the previously reported methodologies involving copper catalysts, reactions have been accomplished without the need of an inert atmosphere and in the absence of solvent, using 1.5 mol% catalyst. A variety of tertiary amines, including aromatic, benzylic and aliphatic ones, have been coupled with both aromatic and aliphatic alkynes to furnish the corresponding propargylamines in moderate-to-excellent yields. The procedure has been successfully scaled-up to 12 mmol with a high conversion (93%). Moreover, the catalyst has been reused in seven cycles maintaining a good performance. Its catalytic activity has been compared with that of an array of commercial copper catalysts, being superior as regards the conversion and minimizing the alkyne homocoupling as a side reaction. The negative filtration test points to a heterogeneous nature of the process. Based on compelling experimental evidence, a novel reaction mechanism has been delineated which outlines the essential role of free radicals and the couple copper(I)/copper(II).
Fil: Alonso, Francisco. Universidad de Alicante. Facultad de Ciencias; España
Fil: Arroyo, Adrian. Universidad de Alicante. Facultad de Ciencias; España
Fil: Martín-García, Iris. Universidad de Alicante. Facultad de Ciencias; España
Fil: Moglie, Yanina Fernanda. Universidad Nacional del Sur. Departamento de Química; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Bahía Blanca. Instituto de Química del Sur; Argentina
description A wide range of catalysts based on supported copper nanoparticles have been prepared and tested in the cross-dehydrogenative coupling of tertiary amines and terminal alkynes. Copper nanoparticles on zeolite Y were found to be the most effective catalyst in the presence of tert-butyl hydroperoxide as the oxidant. Contrary to the previously reported methodologies involving copper catalysts, reactions have been accomplished without the need of an inert atmosphere and in the absence of solvent, using 1.5 mol% catalyst. A variety of tertiary amines, including aromatic, benzylic and aliphatic ones, have been coupled with both aromatic and aliphatic alkynes to furnish the corresponding propargylamines in moderate-to-excellent yields. The procedure has been successfully scaled-up to 12 mmol with a high conversion (93%). Moreover, the catalyst has been reused in seven cycles maintaining a good performance. Its catalytic activity has been compared with that of an array of commercial copper catalysts, being superior as regards the conversion and minimizing the alkyne homocoupling as a side reaction. The negative filtration test points to a heterogeneous nature of the process. Based on compelling experimental evidence, a novel reaction mechanism has been delineated which outlines the essential role of free radicals and the couple copper(I)/copper(II).
publishDate 2015
dc.date.none.fl_str_mv 2015-10
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/11336/4719
Alonso, Francisco; Arroyo, Adrian; Martín-García, Iris; Moglie, Yanina Fernanda; Cross-Dehydrogenative Coupling of Tertiary Amines and Terminal Alkynes Catalyzed by Copper Nanoparticles on Zeolite; Wiley; Advanced Synthesis & Catalysis (print); 357; 16-17; 10-2015; 3549-3561
1615-4150
url http://hdl.handle.net/11336/4719
identifier_str_mv Alonso, Francisco; Arroyo, Adrian; Martín-García, Iris; Moglie, Yanina Fernanda; Cross-Dehydrogenative Coupling of Tertiary Amines and Terminal Alkynes Catalyzed by Copper Nanoparticles on Zeolite; Wiley; Advanced Synthesis & Catalysis (print); 357; 16-17; 10-2015; 3549-3561
1615-4150
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/url/http://onlinelibrary.wiley.com/doi/10.1002/adsc.201500787/abstract
info:eu-repo/semantics/altIdentifier/doi/10.1002/adsc.201500787
info:eu-repo/semantics/altIdentifier/issn/1615-4150
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
eu_rights_str_mv openAccess
rights_invalid_str_mv https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
dc.format.none.fl_str_mv application/pdf
application/pdf
dc.publisher.none.fl_str_mv Wiley
publisher.none.fl_str_mv Wiley
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
_version_ 1842269566786338816
score 13.13397

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