Mechanistic Insight into the Cu-Catalyzed C-S Cross-Coupling of Thioacetate with Aryl Halides. A Joint Experimental-Computational Study

Autores
Soria Castro, Silvia Mercedes; Andrada, Diego Marcelo; Caminos, Daniel Alberto; Argüello, Juan Elias; Robert, Marc; Peñeñory, Alicia Beatriz
Año de publicación
2017
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
The mechanism of the Ullmann-type reaction between potassium thioacetate (KSAc) and iodobenzene (PhI) catalyzed by CuI associated with 1,10-phenanthroline (phen) as a ligand was explored experimentally and computationally. The study on C–S bond formation was investigated by UV–visible spectrophotometry, cyclic voltammetry, mass spectrometry, and products assessment from radical probes. The results indicate that under experimental conditions the catalytically active species is [Cu(phen)(SAc)] regardless of the copper source. An examination of the aryl halide activation mechanism using radical probes was undertaken. No evidence of the presence of radical species was found during the reaction process, which is consistent with an oxidative addition cross-coupling pathway. The different reaction pathways leading to the experimentally observed reaction products were studied by DFT calculation. The oxidative addition–reductive elimination mechanism via an unstable CuIII intermediate is energetically more feasible than other possible mechanisms such as single electron transfer, halogen atom transfer, and σ-bond methatesis.
Fil: Soria Castro, Silvia Mercedes. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina
Fil: Andrada, Diego Marcelo. Philipps-Universität Marburg; Alemania. Universitat Saarland; Alemania. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
Fil: Caminos, Daniel Alberto. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina
Fil: Argüello, Juan Elias. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina
Fil: Robert, Marc. Université Paris Diderot - Paris 7; Francia
Fil: Peñeñory, Alicia Beatriz. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina
Materia
Copper Catalysis
Mechanism
Arilation
Sulfur Nucleophile
Dft
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:11336/43400
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/43400
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Mechanistic Insight into the Cu-Catalyzed C-S Cross-Coupling of Thioacetate with Aryl Halides. A Joint Experimental-Computational StudySoria Castro, Silvia MercedesAndrada, Diego MarceloCaminos, Daniel AlbertoArgüello, Juan EliasRobert, MarcPeñeñory, Alicia BeatrizCopper CatalysisMechanismArilationSulfur NucleophileDfthttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1The mechanism of the Ullmann-type reaction between potassium thioacetate (KSAc) and iodobenzene (PhI) catalyzed by CuI associated with 1,10-phenanthroline (phen) as a ligand was explored experimentally and computationally. The study on C–S bond formation was investigated by UV–visible spectrophotometry, cyclic voltammetry, mass spectrometry, and products assessment from radical probes. The results indicate that under experimental conditions the catalytically active species is [Cu(phen)(SAc)] regardless of the copper source. An examination of the aryl halide activation mechanism using radical probes was undertaken. No evidence of the presence of radical species was found during the reaction process, which is consistent with an oxidative addition cross-coupling pathway. The different reaction pathways leading to the experimentally observed reaction products were studied by DFT calculation. The oxidative addition–reductive elimination mechanism via an unstable CuIII intermediate is energetically more feasible than other possible mechanisms such as single electron transfer, halogen atom transfer, and σ-bond methatesis.Fil: Soria Castro, Silvia Mercedes. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; ArgentinaFil: Andrada, Diego Marcelo. Philipps-Universität Marburg; Alemania. Universitat Saarland; Alemania. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Caminos, Daniel Alberto. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; ArgentinaFil: Argüello, Juan Elias. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; ArgentinaFil: Robert, Marc. Université Paris Diderot - Paris 7; FranciaFil: Peñeñory, Alicia Beatriz. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; ArgentinaAmerican Chemical Society2017-11info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfapplication/pdfapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/43400Soria Castro, Silvia Mercedes; Andrada, Diego Marcelo; Caminos, Daniel Alberto; Argüello, Juan Elias; Robert, Marc; et al.; Mechanistic Insight into the Cu-Catalyzed C-S Cross-Coupling of Thioacetate with Aryl Halides. A Joint Experimental-Computational Study; American Chemical Society; Journal of Organic Chemistry; 82; 21; 11-2017; 11464-114730022-3263CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/http://pubs.acs.org/doi/10.1021/acs.joc.7b01991info:eu-repo/semantics/altIdentifier/doi/10.1021/acs.joc.7b01991info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-10-22T11:22:03Zoai:ri.conicet.gov.ar:11336/43400instacron: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:34982025-10-22 11:22:03.379CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Mechanistic Insight into the Cu-Catalyzed C-S Cross-Coupling of Thioacetate with Aryl Halides. A Joint Experimental-Computational Study
title Mechanistic Insight into the Cu-Catalyzed C-S Cross-Coupling of Thioacetate with Aryl Halides. A Joint Experimental-Computational Study
spellingShingle Mechanistic Insight into the Cu-Catalyzed C-S Cross-Coupling of Thioacetate with Aryl Halides. A Joint Experimental-Computational Study
Soria Castro, Silvia Mercedes
Copper Catalysis
Mechanism
Arilation
Sulfur Nucleophile
Dft
title_short Mechanistic Insight into the Cu-Catalyzed C-S Cross-Coupling of Thioacetate with Aryl Halides. A Joint Experimental-Computational Study
title_full Mechanistic Insight into the Cu-Catalyzed C-S Cross-Coupling of Thioacetate with Aryl Halides. A Joint Experimental-Computational Study
title_fullStr Mechanistic Insight into the Cu-Catalyzed C-S Cross-Coupling of Thioacetate with Aryl Halides. A Joint Experimental-Computational Study
title_full_unstemmed Mechanistic Insight into the Cu-Catalyzed C-S Cross-Coupling of Thioacetate with Aryl Halides. A Joint Experimental-Computational Study
title_sort Mechanistic Insight into the Cu-Catalyzed C-S Cross-Coupling of Thioacetate with Aryl Halides. A Joint Experimental-Computational Study
dc.creator.none.fl_str_mv Soria Castro, Silvia Mercedes
Andrada, Diego Marcelo
Caminos, Daniel Alberto
Argüello, Juan Elias
Robert, Marc
Peñeñory, Alicia Beatriz
author Soria Castro, Silvia Mercedes
author_facet Soria Castro, Silvia Mercedes
Andrada, Diego Marcelo
Caminos, Daniel Alberto
Argüello, Juan Elias
Robert, Marc
Peñeñory, Alicia Beatriz
author_role author
author2 Andrada, Diego Marcelo
Caminos, Daniel Alberto
Argüello, Juan Elias
Robert, Marc
Peñeñory, Alicia Beatriz
author2_role author
author
author
author
author
dc.subject.none.fl_str_mv Copper Catalysis
Mechanism
Arilation
Sulfur Nucleophile
Dft
topic Copper Catalysis
Mechanism
Arilation
Sulfur Nucleophile
Dft
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv The mechanism of the Ullmann-type reaction between potassium thioacetate (KSAc) and iodobenzene (PhI) catalyzed by CuI associated with 1,10-phenanthroline (phen) as a ligand was explored experimentally and computationally. The study on C–S bond formation was investigated by UV–visible spectrophotometry, cyclic voltammetry, mass spectrometry, and products assessment from radical probes. The results indicate that under experimental conditions the catalytically active species is [Cu(phen)(SAc)] regardless of the copper source. An examination of the aryl halide activation mechanism using radical probes was undertaken. No evidence of the presence of radical species was found during the reaction process, which is consistent with an oxidative addition cross-coupling pathway. The different reaction pathways leading to the experimentally observed reaction products were studied by DFT calculation. The oxidative addition–reductive elimination mechanism via an unstable CuIII intermediate is energetically more feasible than other possible mechanisms such as single electron transfer, halogen atom transfer, and σ-bond methatesis.
Fil: Soria Castro, Silvia Mercedes. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina
Fil: Andrada, Diego Marcelo. Philipps-Universität Marburg; Alemania. Universitat Saarland; Alemania. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
Fil: Caminos, Daniel Alberto. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina
Fil: Argüello, Juan Elias. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina
Fil: Robert, Marc. Université Paris Diderot - Paris 7; Francia
Fil: Peñeñory, Alicia Beatriz. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina
description The mechanism of the Ullmann-type reaction between potassium thioacetate (KSAc) and iodobenzene (PhI) catalyzed by CuI associated with 1,10-phenanthroline (phen) as a ligand was explored experimentally and computationally. The study on C–S bond formation was investigated by UV–visible spectrophotometry, cyclic voltammetry, mass spectrometry, and products assessment from radical probes. The results indicate that under experimental conditions the catalytically active species is [Cu(phen)(SAc)] regardless of the copper source. An examination of the aryl halide activation mechanism using radical probes was undertaken. No evidence of the presence of radical species was found during the reaction process, which is consistent with an oxidative addition cross-coupling pathway. The different reaction pathways leading to the experimentally observed reaction products were studied by DFT calculation. The oxidative addition–reductive elimination mechanism via an unstable CuIII intermediate is energetically more feasible than other possible mechanisms such as single electron transfer, halogen atom transfer, and σ-bond methatesis.
publishDate 2017
dc.date.none.fl_str_mv 2017-11
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/11336/43400
Soria Castro, Silvia Mercedes; Andrada, Diego Marcelo; Caminos, Daniel Alberto; Argüello, Juan Elias; Robert, Marc; et al.; Mechanistic Insight into the Cu-Catalyzed C-S Cross-Coupling of Thioacetate with Aryl Halides. A Joint Experimental-Computational Study; American Chemical Society; Journal of Organic Chemistry; 82; 21; 11-2017; 11464-11473
0022-3263
CONICET Digital
CONICET
url http://hdl.handle.net/11336/43400
identifier_str_mv Soria Castro, Silvia Mercedes; Andrada, Diego Marcelo; Caminos, Daniel Alberto; Argüello, Juan Elias; Robert, Marc; et al.; Mechanistic Insight into the Cu-Catalyzed C-S Cross-Coupling of Thioacetate with Aryl Halides. A Joint Experimental-Computational Study; American Chemical Society; Journal of Organic Chemistry; 82; 21; 11-2017; 11464-11473
0022-3263
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/url/http://pubs.acs.org/doi/10.1021/acs.joc.7b01991
info:eu-repo/semantics/altIdentifier/doi/10.1021/acs.joc.7b01991
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
application/pdf
application/pdf
application/pdf
dc.publisher.none.fl_str_mv American Chemical Society
publisher.none.fl_str_mv American Chemical Society
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 12.982451

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