Zn(II) Byproduct Enhances the Cu-Catalyzed Cross-Coupling of Bromozinc Difluorophosphonate with Iodobenzoates: A DFT Study

The copper-catalyzed cross-coupling of bromozinc difluorophosphonate with iodobenzoates has been studied with the DFT methodology in order to understand the experimentally observed reactivity. The directing carboxylate group promotes the reaction for methyl 2-iodobenzoate and, unexpectedly, also for...

Descripción completa

Detalles Bibliográficos
Autor: Jover Modrego, Jesús
Tipo de recurso: artículo
Estado:Versión aceptada para publicación
Fecha de publicación:2018
País:España
Institución:Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)
Repositorio:Recercat. Dipósit de la Recerca de Catalunya
OAI Identifier:oai:recercat.cat:2445/142919
Acceso en línea:https://hdl.handle.net/2445/142919
Access Level:acceso abierto
Palabra clave:Catalitzadors
Coure
Catalysts
Copper
id ES_6cb3c22cfceedf17cb8329c350ecba79
oai_identifier_str oai:recercat.cat:2445/142919
network_acronym_str ES
network_name_str España
repository_id_str
spelling Zn(II) Byproduct Enhances the Cu-Catalyzed Cross-Coupling of Bromozinc Difluorophosphonate with Iodobenzoates: A DFT StudyJover Modrego, JesúsCatalitzadorsCoureCatalystsCopperThe copper-catalyzed cross-coupling of bromozinc difluorophosphonate with iodobenzoates has been studied with the DFT methodology in order to understand the experimentally observed reactivity. The directing carboxylate group promotes the reaction for methyl 2-iodobenzoate and, unexpectedly, also for methyl 4-iodobenzoate, although to a lesser extent. DFT calculations show that the Zn(II) byproduct, formed in the initial stages of the reaction, remains attached to the catalyst and serves as an anchoring point for the benzoate moiety, allowing in turn the reaction for both ortho- and para-substituted iodobenzoates. The computationally derived reaction mechanism has also been applied to study whether other substrates may engage in a similar cross-coupling process with bromozinc difluorophosphonate. The calculations carried out on substrates bearing nitrogen-directing groups, such as triazene and pyridine, indicate that their reactions should be possible and that the latter should produce a much faster reaction in comparison to iodobenzoates.American Chemical Society2019201920182019info:eu-repo/semantics/articleinfo:eu-repo/semantics/acceptedVersion10 p.application/pdfhttps://hdl.handle.net/2445/142919Articles publicats en revistes (Química Inorgànica i Orgànica)reponame:Recercat. Dipósit de la Recerca de Catalunyainstname:Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)InglésVersió postprint del document publicat a: https://doi.org/10.1021/acs.organomet.7b00739Organometallics, 2018, vol. 37, num. 3, p. 327-336https://doi.org/10.1021/acs.organomet.7b00739(c) American Chemical Society , 2018info:eu-repo/semantics/openAccessoai:recercat.cat:2445/1429192026-05-29T05:05:01Z
dc.title.none.fl_str_mv Zn(II) Byproduct Enhances the Cu-Catalyzed Cross-Coupling of Bromozinc Difluorophosphonate with Iodobenzoates: A DFT Study
title Zn(II) Byproduct Enhances the Cu-Catalyzed Cross-Coupling of Bromozinc Difluorophosphonate with Iodobenzoates: A DFT Study
spellingShingle Zn(II) Byproduct Enhances the Cu-Catalyzed Cross-Coupling of Bromozinc Difluorophosphonate with Iodobenzoates: A DFT Study
Jover Modrego, Jesús
Catalitzadors
Coure
Catalysts
Copper
title_short Zn(II) Byproduct Enhances the Cu-Catalyzed Cross-Coupling of Bromozinc Difluorophosphonate with Iodobenzoates: A DFT Study
title_full Zn(II) Byproduct Enhances the Cu-Catalyzed Cross-Coupling of Bromozinc Difluorophosphonate with Iodobenzoates: A DFT Study
title_fullStr Zn(II) Byproduct Enhances the Cu-Catalyzed Cross-Coupling of Bromozinc Difluorophosphonate with Iodobenzoates: A DFT Study
title_full_unstemmed Zn(II) Byproduct Enhances the Cu-Catalyzed Cross-Coupling of Bromozinc Difluorophosphonate with Iodobenzoates: A DFT Study
title_sort Zn(II) Byproduct Enhances the Cu-Catalyzed Cross-Coupling of Bromozinc Difluorophosphonate with Iodobenzoates: A DFT Study
dc.creator.none.fl_str_mv Jover Modrego, Jesús
author Jover Modrego, Jesús
author_facet Jover Modrego, Jesús
author_role author
dc.subject.none.fl_str_mv Catalitzadors
Coure
Catalysts
Copper
topic Catalitzadors
Coure
Catalysts
Copper
description The copper-catalyzed cross-coupling of bromozinc difluorophosphonate with iodobenzoates has been studied with the DFT methodology in order to understand the experimentally observed reactivity. The directing carboxylate group promotes the reaction for methyl 2-iodobenzoate and, unexpectedly, also for methyl 4-iodobenzoate, although to a lesser extent. DFT calculations show that the Zn(II) byproduct, formed in the initial stages of the reaction, remains attached to the catalyst and serves as an anchoring point for the benzoate moiety, allowing in turn the reaction for both ortho- and para-substituted iodobenzoates. The computationally derived reaction mechanism has also been applied to study whether other substrates may engage in a similar cross-coupling process with bromozinc difluorophosphonate. The calculations carried out on substrates bearing nitrogen-directing groups, such as triazene and pyridine, indicate that their reactions should be possible and that the latter should produce a much faster reaction in comparison to iodobenzoates.
publishDate 2018
dc.date.none.fl_str_mv 2018
2019
2019
2019
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/acceptedVersion
format article
status_str acceptedVersion
dc.identifier.none.fl_str_mv https://hdl.handle.net/2445/142919
url https://hdl.handle.net/2445/142919
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv Versió postprint del document publicat a: https://doi.org/10.1021/acs.organomet.7b00739
Organometallics, 2018, vol. 37, num. 3, p. 327-336
https://doi.org/10.1021/acs.organomet.7b00739
dc.rights.none.fl_str_mv (c) American Chemical Society , 2018
info:eu-repo/semantics/openAccess
rights_invalid_str_mv (c) American Chemical Society , 2018
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv 10 p.
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 Articles publicats en revistes (Química Inorgànica i Orgànica)
reponame:Recercat. Dipósit de la Recerca de Catalunya
instname:Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)
instname_str Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)
reponame_str Recercat. Dipósit de la Recerca de Catalunya
collection Recercat. Dipósit de la Recerca de Catalunya
repository.name.fl_str_mv
repository.mail.fl_str_mv
_version_ 1869410287091712000
score 15,81155

Similares en LA Referencia