The transmetalation step in Pd-catalyzed processes: understanding the role of the classical nucleophile, the ligands and the synthetic potential of a third metal

The transmetalation step of Pd-catalyzed reactions is studied in-depth in this Doctoral Thesis. New bimetallic systems based on the Au/Pd and the Cu/Pd couple have been developed in the context of the Stille reaction and the Hiyama reaction that are very efficient for the coupling of bulky groups. T...

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Autor: Pozo del Valle, Juan del
Tipo de recurso: tesis doctoral
Estado:Versión publicada
Fecha de publicación:2016
País:España
Institución:Universidad de Valladolid
Repositorio:UVaDOC. Repositorio Documental de la Universidad de Valladolid
OAI Identifier:oai:uvadoc.uva.es:10324/39306
Acceso en línea:https://doi.org/10.35376/10324/39306
http://uvadoc.uva.es/handle/10324/39306
Access Level:acceso abierto
Palabra clave:2303 Química Inorgánica
2306 Química Orgánica
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spelling The transmetalation step in Pd-catalyzed processes: understanding the role of the classical nucleophile, the ligands and the synthetic potential of a third metalPozo del Valle, Juan del2303 Química Inorgánica2306 Química OrgánicaThe transmetalation step of Pd-catalyzed reactions is studied in-depth in this Doctoral Thesis. New bimetallic systems based on the Au/Pd and the Cu/Pd couple have been developed in the context of the Stille reaction and the Hiyama reaction that are very efficient for the coupling of bulky groups. This type of couplings are very challenging with other methodologies and provide excellent results under a synthetic point of view with our bimetallic approach. The bimetallic systems have been examined under a mechanistic point of view. The role of the cocatalyst, the auxiliary ligands and the tin and silicon organometallics have been understood, providing relevant information for the improvement of these systems and the development of new others. The secondary transmetalations that lead to undesired byproducts in the Negishi reaction have been studied in detail by experimental and computational techniques. The information obtained in our study provides important information that will contribute to develop more efficient Negishi reactions. A ligand designed in our group to promote challenging reductive eliminations has been tested for the Pd-catalyzed fluorination and trifluoromethylation of aryl halides. The ligand is not effective for this reaction due to the existence of a migratory insertion process that prevents the desired reductive elimination. This process has been studied by DFT calculations. The mechanisms of the N-H activation of anilines by Ir(PCP) complexes has been carried out by experimental and computational techniques. The information obtained will be used to design more efficient reactions based on this activation.Departamento de Química Física y Química InorgánicaDoctorado en Química: Química de Síntesis, Catálisis y Materiales AvanzadosEspinet Rubio, PabloCasares González, Juan ÁngelUniversidad de Valladolid. Facultad de Ciencias2016info:eu-repo/semantics/doctoralThesisinfo:eu-repo/semantics/publishedVersionapplication/pdfhttps://doi.org/10.35376/10324/39306http://uvadoc.uva.es/handle/10324/39306reponame:UVaDOC. Repositorio Documental de la Universidad de Valladolidinstname:Universidad de ValladolidInglésinfo:eu-repo/semantics/openAccesshttp://creativecommons.org/licenses/by-nc-nd/4.0/oai:uvadoc.uva.es:10324/393062026-06-13T12:44:47Z
dc.title.none.fl_str_mv The transmetalation step in Pd-catalyzed processes: understanding the role of the classical nucleophile, the ligands and the synthetic potential of a third metal
title The transmetalation step in Pd-catalyzed processes: understanding the role of the classical nucleophile, the ligands and the synthetic potential of a third metal
spellingShingle The transmetalation step in Pd-catalyzed processes: understanding the role of the classical nucleophile, the ligands and the synthetic potential of a third metal
Pozo del Valle, Juan del
2303 Química Inorgánica
2306 Química Orgánica
title_short The transmetalation step in Pd-catalyzed processes: understanding the role of the classical nucleophile, the ligands and the synthetic potential of a third metal
title_full The transmetalation step in Pd-catalyzed processes: understanding the role of the classical nucleophile, the ligands and the synthetic potential of a third metal
title_fullStr The transmetalation step in Pd-catalyzed processes: understanding the role of the classical nucleophile, the ligands and the synthetic potential of a third metal
title_full_unstemmed The transmetalation step in Pd-catalyzed processes: understanding the role of the classical nucleophile, the ligands and the synthetic potential of a third metal
title_sort The transmetalation step in Pd-catalyzed processes: understanding the role of the classical nucleophile, the ligands and the synthetic potential of a third metal
dc.creator.none.fl_str_mv Pozo del Valle, Juan del
author Pozo del Valle, Juan del
author_facet Pozo del Valle, Juan del
author_role author
dc.contributor.none.fl_str_mv Espinet Rubio, Pablo
Casares González, Juan Ángel
Universidad de Valladolid. Facultad de Ciencias
dc.subject.none.fl_str_mv 2303 Química Inorgánica
2306 Química Orgánica
topic 2303 Química Inorgánica
2306 Química Orgánica
description The transmetalation step of Pd-catalyzed reactions is studied in-depth in this Doctoral Thesis. New bimetallic systems based on the Au/Pd and the Cu/Pd couple have been developed in the context of the Stille reaction and the Hiyama reaction that are very efficient for the coupling of bulky groups. This type of couplings are very challenging with other methodologies and provide excellent results under a synthetic point of view with our bimetallic approach. The bimetallic systems have been examined under a mechanistic point of view. The role of the cocatalyst, the auxiliary ligands and the tin and silicon organometallics have been understood, providing relevant information for the improvement of these systems and the development of new others. The secondary transmetalations that lead to undesired byproducts in the Negishi reaction have been studied in detail by experimental and computational techniques. The information obtained in our study provides important information that will contribute to develop more efficient Negishi reactions. A ligand designed in our group to promote challenging reductive eliminations has been tested for the Pd-catalyzed fluorination and trifluoromethylation of aryl halides. The ligand is not effective for this reaction due to the existence of a migratory insertion process that prevents the desired reductive elimination. This process has been studied by DFT calculations. The mechanisms of the N-H activation of anilines by Ir(PCP) complexes has been carried out by experimental and computational techniques. The information obtained will be used to design more efficient reactions based on this activation.
publishDate 2016
dc.date.none.fl_str_mv 2016
dc.type.none.fl_str_mv info:eu-repo/semantics/doctoralThesis
info:eu-repo/semantics/publishedVersion
format doctoralThesis
status_str publishedVersion
dc.identifier.none.fl_str_mv https://doi.org/10.35376/10324/39306
http://uvadoc.uva.es/handle/10324/39306
url https://doi.org/10.35376/10324/39306
http://uvadoc.uva.es/handle/10324/39306
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
http://creativecommons.org/licenses/by-nc-nd/4.0/
eu_rights_str_mv openAccess
rights_invalid_str_mv http://creativecommons.org/licenses/by-nc-nd/4.0/
dc.format.none.fl_str_mv application/pdf
dc.source.none.fl_str_mv reponame:UVaDOC. Repositorio Documental de la Universidad de Valladolid
instname:Universidad de Valladolid
instname_str Universidad de Valladolid
reponame_str UVaDOC. Repositorio Documental de la Universidad de Valladolid
collection UVaDOC. Repositorio Documental de la Universidad de Valladolid
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repository.mail.fl_str_mv
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