A Tribute to Ullmann’s Work: Expanding Copper Coil Reactor Applications toward the Hydroxylation of Aryl Bromides

Copper coil flow reactors represent an economic, abundant, and durable platform for conducting copper-catalyzed reactions. These have been used in the past for Ullmann-type reactions starting from aryl iodides. However, no procedures have been described for the activation of less reactive aryl bromi...

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Autores: Molins Colomer, Maite, FERNANDEZ, JAVIER, Berzosa, Xavier
Tipo de recurso: artículo
Fecha de publicación:2024
País:España
Institución:Universitat Ramon Llull (URL)
Repositorio:DAU Arxiu Digital de la Universitat Ramon Llull
OAI Identifier:oai:dau.url.edu:20.500.14342/5298
Acceso en línea:https://hdl.handle.net/20.500.14342/5298
https://doi.org/10.1021/acs.oprd.4c00402
Access Level:acceso abierto
Palabra clave:aryl halides
C−O bond formation
copper
flow chemistry
hydroxylation
phenols
544
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spelling A Tribute to Ullmann’s Work: Expanding Copper Coil Reactor Applications toward the Hydroxylation of Aryl BromidesMolins Colomer, MaiteFERNANDEZ, JAVIERBerzosa, Xavieraryl halidesC−O bond formationcopperflow chemistryhydroxylationphenols544Copper coil flow reactors represent an economic, abundant, and durable platform for conducting copper-catalyzed reactions. These have been used in the past for Ullmann-type reactions starting from aryl iodides. However, no procedures have been described for the activation of less reactive aryl bromides. In this work, we successfully developed a method for the hydroxylation of aryl bromides promoted by a copper coil reactor. Notably, the presence of both a diamine ligand and DMF is key for the reaction to proceed. An inorganic base such as Na2CO3 also improved the reaction yield by minimizing the formation of side products. The setup has been applied to a range of disubstituted aryl bromides in moderate to good yields and was tested under 24 h of continuous operation, showing stable yields, thus proving the robustness of the catalysis. Finally, the lifetime of a copper reactor operating under the described conditions has been calculated for the first time, proving that this technology is safe to operate at an industrial scale.info:eu-repo/semantics/publishedVersionAmerican Chemical SocietyUniversitat Ramon Llull. IQS202520252024info:eu-repo/semantics/article8 p.application/pdfhttps://hdl.handle.net/20.500.14342/5298https://doi.org/10.1021/acs.oprd.4c00402reponame:DAU Arxiu Digital de la Universitat Ramon Llullinstname:Universitat Ramon Llull (URL)InglésOrganic Process Research & Development. 2024;28(12):4477-4484info:eu-repo/grantAgreement/SUR del DEC/SGR/2021 SGR 00520info:eu-repo/grantAgreement/SUR del DEC/SGR/2021 SGR 00321info:eu-repo/grantAgreement/MICIU/FPU/21© L'autor/aAttribution 4.0 Internationalhttp://creativecommons.org/licenses/by/4.0/info:eu-repo/semantics/openAccessoai:dau.url.edu:20.500.14342/52982026-06-21T06:40:37Z
dc.title.none.fl_str_mv A Tribute to Ullmann’s Work: Expanding Copper Coil Reactor Applications toward the Hydroxylation of Aryl Bromides
title A Tribute to Ullmann’s Work: Expanding Copper Coil Reactor Applications toward the Hydroxylation of Aryl Bromides
spellingShingle A Tribute to Ullmann’s Work: Expanding Copper Coil Reactor Applications toward the Hydroxylation of Aryl Bromides
Molins Colomer, Maite
aryl halides
C−O bond formation
copper
flow chemistry
hydroxylation
phenols
544
title_short A Tribute to Ullmann’s Work: Expanding Copper Coil Reactor Applications toward the Hydroxylation of Aryl Bromides
title_full A Tribute to Ullmann’s Work: Expanding Copper Coil Reactor Applications toward the Hydroxylation of Aryl Bromides
title_fullStr A Tribute to Ullmann’s Work: Expanding Copper Coil Reactor Applications toward the Hydroxylation of Aryl Bromides
title_full_unstemmed A Tribute to Ullmann’s Work: Expanding Copper Coil Reactor Applications toward the Hydroxylation of Aryl Bromides
title_sort A Tribute to Ullmann’s Work: Expanding Copper Coil Reactor Applications toward the Hydroxylation of Aryl Bromides
dc.creator.none.fl_str_mv Molins Colomer, Maite
FERNANDEZ, JAVIER
Berzosa, Xavier
author Molins Colomer, Maite
author_facet Molins Colomer, Maite
FERNANDEZ, JAVIER
Berzosa, Xavier
author_role author
author2 FERNANDEZ, JAVIER
Berzosa, Xavier
author2_role author
author
dc.contributor.none.fl_str_mv Universitat Ramon Llull. IQS
dc.subject.none.fl_str_mv aryl halides
C−O bond formation
copper
flow chemistry
hydroxylation
phenols
544
topic aryl halides
C−O bond formation
copper
flow chemistry
hydroxylation
phenols
544
description Copper coil flow reactors represent an economic, abundant, and durable platform for conducting copper-catalyzed reactions. These have been used in the past for Ullmann-type reactions starting from aryl iodides. However, no procedures have been described for the activation of less reactive aryl bromides. In this work, we successfully developed a method for the hydroxylation of aryl bromides promoted by a copper coil reactor. Notably, the presence of both a diamine ligand and DMF is key for the reaction to proceed. An inorganic base such as Na2CO3 also improved the reaction yield by minimizing the formation of side products. The setup has been applied to a range of disubstituted aryl bromides in moderate to good yields and was tested under 24 h of continuous operation, showing stable yields, thus proving the robustness of the catalysis. Finally, the lifetime of a copper reactor operating under the described conditions has been calculated for the first time, proving that this technology is safe to operate at an industrial scale.
publishDate 2024
dc.date.none.fl_str_mv 2024
2025
2025
dc.type.none.fl_str_mv info:eu-repo/semantics/article
format article
dc.identifier.none.fl_str_mv https://hdl.handle.net/20.500.14342/5298
https://doi.org/10.1021/acs.oprd.4c00402
url https://hdl.handle.net/20.500.14342/5298
https://doi.org/10.1021/acs.oprd.4c00402
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv Organic Process Research & Development. 2024;28(12):4477-4484
info:eu-repo/grantAgreement/SUR del DEC/SGR/2021 SGR 00520
info:eu-repo/grantAgreement/SUR del DEC/SGR/2021 SGR 00321
info:eu-repo/grantAgreement/MICIU/FPU/21
dc.rights.none.fl_str_mv © L'autor/a
Attribution 4.0 International
http://creativecommons.org/licenses/by/4.0/
info:eu-repo/semantics/openAccess
rights_invalid_str_mv © L'autor/a
Attribution 4.0 International
http://creativecommons.org/licenses/by/4.0/
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv 8 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 reponame:DAU Arxiu Digital de la Universitat Ramon Llull
instname:Universitat Ramon Llull (URL)
instname_str Universitat Ramon Llull (URL)
reponame_str DAU Arxiu Digital de la Universitat Ramon Llull
collection DAU Arxiu Digital de la Universitat Ramon Llull
repository.name.fl_str_mv
repository.mail.fl_str_mv
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score 15,81155

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