Highly Efficient Production of Heteroarene Phosphonates by Dichromatic Photoredox Catalysis

[EN] A new strategy to achieve efficient aerobic phosphorylation of five-membered heteraroenes with excellent yields using dichromatic photoredox catalysis in a gel-based nanoreactor is described here. The procedure involves visible aerobic irradiation (cold white LEDs) of a mixture containing the h...

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Autores: Herrera-Luna, Jorge Carlos|||0000-0003-2992-7339, Jiménez, M Consuelo|||0000-0002-8057-4316, Pérez-Ruiz, Raúl|||0000-0003-1136-3598, Díaz Díaz, David
Tipo de recurso: artículo
Fecha de publicación:2021
País:España
Institución:Universitat Politècnica de València (UPV)
Repositorio:RiuNet. Repositorio Institucional de la Universitat Politécnica de Valéncia
Idioma:inglés
OAI Identifier:oai:riunet.upv.es:10251/188472
Acceso en línea:https://riunet.upv.es/handle/10251/188472
Access Level:acceso abierto
Palabra clave:Dichromatic photocatalysis
Visible light
Gel nanoreactor
Heteroarene halides
Phosphorylation
QUIMICA ORGANICA
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oai_identifier_str oai:riunet.upv.es:10251/188472
network_acronym_str ES
network_name_str España
repository_id_str
dc.title.none.fl_str_mv Highly Efficient Production of Heteroarene Phosphonates by Dichromatic Photoredox Catalysis
title Highly Efficient Production of Heteroarene Phosphonates by Dichromatic Photoredox Catalysis
spellingShingle Highly Efficient Production of Heteroarene Phosphonates by Dichromatic Photoredox Catalysis
Herrera-Luna, Jorge Carlos|||0000-0003-2992-7339
Dichromatic photocatalysis
Visible light
Gel nanoreactor
Heteroarene halides
Phosphorylation
QUIMICA ORGANICA
title_short Highly Efficient Production of Heteroarene Phosphonates by Dichromatic Photoredox Catalysis
title_full Highly Efficient Production of Heteroarene Phosphonates by Dichromatic Photoredox Catalysis
title_fullStr Highly Efficient Production of Heteroarene Phosphonates by Dichromatic Photoredox Catalysis
title_full_unstemmed Highly Efficient Production of Heteroarene Phosphonates by Dichromatic Photoredox Catalysis
title_sort Highly Efficient Production of Heteroarene Phosphonates by Dichromatic Photoredox Catalysis
dc.creator.none.fl_str_mv Herrera-Luna, Jorge Carlos|||0000-0003-2992-7339
Jiménez, M Consuelo|||0000-0002-8057-4316
Pérez-Ruiz, Raúl|||0000-0003-1136-3598
Díaz Díaz, David
author Herrera-Luna, Jorge Carlos|||0000-0003-2992-7339
author_facet Herrera-Luna, Jorge Carlos|||0000-0003-2992-7339
Jiménez, M Consuelo|||0000-0002-8057-4316
Pérez-Ruiz, Raúl|||0000-0003-1136-3598
Díaz Díaz, David
author_role author
author2 Jiménez, M Consuelo|||0000-0002-8057-4316
Pérez-Ruiz, Raúl|||0000-0003-1136-3598
Díaz Díaz, David
author2_role author
author
author
dc.contributor.none.fl_str_mv Departamento de Química
Escuela Técnica Superior de Ingeniería Industrial
Grupo de estudio de estados excitados: detección, dinámica, transformaciones y campos de aplicación
GENERALITAT VALENCIANA
AGENCIA ESTATAL DE INVESTIGACION
Ministerio de Ciencia, Innovación y Universidades
Repositorio Institucional de la Universitat Politècnica de València Riunet
dc.subject.none.fl_str_mv Dichromatic photocatalysis
Visible light
Gel nanoreactor
Heteroarene halides
Phosphorylation
QUIMICA ORGANICA
topic Dichromatic photocatalysis
Visible light
Gel nanoreactor
Heteroarene halides
Phosphorylation
QUIMICA ORGANICA
description [EN] A new strategy to achieve efficient aerobic phosphorylation of five-membered heteraroenes with excellent yields using dichromatic photoredox catalysis in a gel-based nanoreactor is described here. The procedure involves visible aerobic irradiation (cold white LEDs) of a mixture containing the heteroarene halide, trisubstituted phospite, N,N-diisopropylethylamine (DIPEA) as sacrificial agent, and catalytic amounts of 9,10-dicyanoanthracene (DCA) in the presence of an adequate gelator, which permits a faster process than at the homogeneous phase. The methodology, which operates by a consecutive photoinduced electron transfer (ConPET) mechanism, has been successfully applied to the straightforward and clean synthesis of a number of different heteroarene (furan, thiophene, selenophene, pyrrole, oxazole, or thioxazole) phosphonates, extending to the late-stage phosphonylation of the anticoagulant rivaroxaban. Strategically, employment of cold white light is critical since it provides both selective wavelengths for exciting first DCA (blue region) and subsequently its corresponding radical anion DCA(center dot-) (green region). The resultant strongly reducing excited agent DCA(center dot-)* is capable of even activate five-membered heteroarene halides (Br, Cl) with high reduction potentials (similar to-2.7 V) to effect the C(sp(2))-P bond formation. Spectroscopic and thermodynamic studies have supported the proposed reaction mechanism. Interestingly, the rate of product formation has been clearly enhanced in gel media because reactants can be presumably localized not only in the solvent pools but also through to the fibers of the viscoelastic gel network. This has been confirmed by field-emission scanning electron microscopy images where a marked densification of the network has been observed, modifying its fibrillary morphology. Finally, rheological measurements have shown the resistance of the gel network to the incorporation of the reactants and the formation of the desired products.
publishDate 2021
dc.date.none.fl_str_mv 2021
2021-10-07
dc.type.none.fl_str_mv journal article
http://purl.org/coar/resource_type/c_6501
VoR
http://purl.org/coar/version/c_970fb48d4fbd8a85
dc.type.openaire.fl_str_mv info:eu-repo/semantics/article
format article
dc.identifier.none.fl_str_mv https://riunet.upv.es/handle/10251/188472
url https://riunet.upv.es/handle/10251/188472
dc.language.none.fl_str_mv Inglés
eng
language_invalid_str_mv Inglés
language eng
dc.relation.none.fl_str_mv Agencia Estatal de Investigación http://dx.doi.org/10.13039/501100011033 Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020 PID2019-105391GB-C22 DESARROLLO DE NUEVOS SISTEMAS DE CONVERSION BIFOTONICA A MAYOR FRECUENCIA BASADOS EN ANIQUILACION TRIPLETE-TRIPLETE PARA FOTOCATALISIS REDOX CON LUZ VISIBLE
Ministerio de Ciencia, Innovación y Universidades https://doi.org/10.13039/100014440 BEAGAL18%2F00166
Agencia Estatal de Investigación http://dx.doi.org/10.13039/501100011033 BES-2017-080215 AYUDA PARA CONTRATOS PREDOCTORALES PARA LA FORMACION DE DOCTORES 2017-HERRERA LUNA. PROYECTO: CONTROL SUPRAMOLECULAR DE LA FOTORREACTIVIDAD EN MEDIOS MICROHETEROGENOS BASADOS EN AMINOACIDOS
Generalitat Valenciana https://doi.org/10.13039/501100003359 CIDEGENT%2F2018%2F044 AYUDA CIDEGENT CONTRATACION RAUL PEREZ RUIZ
Generalitat Valenciana https://doi.org/10.13039/501100003359 CIDEGENT%2F2018%2F044 PHOTON UPCONVERSION REDOX CATALYSIS
dc.rights.none.fl_str_mv open access
http://purl.org/coar/access_right/c_abf2
Reconocimiento (by)
http://creativecommons.org/licenses/by/4.0/
dc.rights.openaire.fl_str_mv info:eu-repo/semantics/openAccess
rights_invalid_str_mv open access
http://purl.org/coar/access_right/c_abf2
Reconocimiento (by)
http://creativecommons.org/licenses/by/4.0/
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv 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:RiuNet. Repositorio Institucional de la Universitat Politécnica de Valéncia
instname:Universitat Politècnica de València (UPV)
instname_str Universitat Politècnica de València (UPV)
reponame_str RiuNet. Repositorio Institucional de la Universitat Politécnica de Valéncia
collection RiuNet. Repositorio Institucional de la Universitat Politécnica de Valéncia
repository.name.fl_str_mv
repository.mail.fl_str_mv
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spelling Highly Efficient Production of Heteroarene Phosphonates by Dichromatic Photoredox CatalysisHerrera-Luna, Jorge Carlos|||0000-0003-2992-7339Jiménez, M Consuelo|||0000-0002-8057-4316Pérez-Ruiz, Raúl|||0000-0003-1136-3598Díaz Díaz, DavidDichromatic photocatalysisVisible lightGel nanoreactorHeteroarene halidesPhosphorylationQUIMICA ORGANICA[EN] A new strategy to achieve efficient aerobic phosphorylation of five-membered heteraroenes with excellent yields using dichromatic photoredox catalysis in a gel-based nanoreactor is described here. The procedure involves visible aerobic irradiation (cold white LEDs) of a mixture containing the heteroarene halide, trisubstituted phospite, N,N-diisopropylethylamine (DIPEA) as sacrificial agent, and catalytic amounts of 9,10-dicyanoanthracene (DCA) in the presence of an adequate gelator, which permits a faster process than at the homogeneous phase. The methodology, which operates by a consecutive photoinduced electron transfer (ConPET) mechanism, has been successfully applied to the straightforward and clean synthesis of a number of different heteroarene (furan, thiophene, selenophene, pyrrole, oxazole, or thioxazole) phosphonates, extending to the late-stage phosphonylation of the anticoagulant rivaroxaban. Strategically, employment of cold white light is critical since it provides both selective wavelengths for exciting first DCA (blue region) and subsequently its corresponding radical anion DCA(center dot-) (green region). The resultant strongly reducing excited agent DCA(center dot-)* is capable of even activate five-membered heteroarene halides (Br, Cl) with high reduction potentials (similar to-2.7 V) to effect the C(sp(2))-P bond formation. Spectroscopic and thermodynamic studies have supported the proposed reaction mechanism. Interestingly, the rate of product formation has been clearly enhanced in gel media because reactants can be presumably localized not only in the solvent pools but also through to the fibers of the viscoelastic gel network. This has been confirmed by field-emission scanning electron microscopy images where a marked densification of the network has been observed, modifying its fibrillary morphology. Finally, rheological measurements have shown the resistance of the gel network to the incorporation of the reactants and the formation of the desired products.Financial support from the Generalitat Valenciana (CIDEGENT/2018/044) and the Spanish Ministry of Science and Innovation (PID2019-105391GB-C21, PID2019-105391GBC22, BES-2017-080215, and BEAGAL18/00166) is gratefully acknowledged. D.D.D. thanks NANOTech., INTech, Cabildo de Tenerife, and ULL for laboratory facilities. We also thank the Electron Microscopy Service from the UPV.American Chemical SocietyDepartamento de QuímicaEscuela Técnica Superior de Ingeniería IndustrialGrupo de estudio de estados excitados: detección, dinámica, transformaciones y campos de aplicaciónGENERALITAT VALENCIANAAGENCIA ESTATAL DE INVESTIGACIONMinisterio de Ciencia, Innovación y UniversidadesRepositorio Institucional de la Universitat Politècnica de València Riunet20212021-10-07journal articlehttp://purl.org/coar/resource_type/c_6501VoRhttp://purl.org/coar/version/c_970fb48d4fbd8a85info:eu-repo/semantics/articleapplication/pdfhttps://riunet.upv.es/handle/10251/188472reponame:RiuNet. Repositorio Institucional de la Universitat Politécnica de Valénciainstname:Universitat Politècnica de València (UPV)InglésengAgencia Estatal de Investigación http://dx.doi.org/10.13039/501100011033 Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020 PID2019-105391GB-C22 DESARROLLO DE NUEVOS SISTEMAS DE CONVERSION BIFOTONICA A MAYOR FRECUENCIA BASADOS EN ANIQUILACION TRIPLETE-TRIPLETE PARA FOTOCATALISIS REDOX CON LUZ VISIBLEMinisterio de Ciencia, Innovación y Universidades https://doi.org/10.13039/100014440 BEAGAL18%2F00166Agencia Estatal de Investigación http://dx.doi.org/10.13039/501100011033 BES-2017-080215 AYUDA PARA CONTRATOS PREDOCTORALES PARA LA FORMACION DE DOCTORES 2017-HERRERA LUNA. PROYECTO: CONTROL SUPRAMOLECULAR DE LA FOTORREACTIVIDAD EN MEDIOS MICROHETEROGENOS BASADOS EN AMINOACIDOSGeneralitat Valenciana https://doi.org/10.13039/501100003359 CIDEGENT%2F2018%2F044 AYUDA CIDEGENT CONTRATACION RAUL PEREZ RUIZGeneralitat Valenciana https://doi.org/10.13039/501100003359 CIDEGENT%2F2018%2F044 PHOTON UPCONVERSION REDOX CATALYSISopen accesshttp://purl.org/coar/access_right/c_abf2Reconocimiento (by)http://creativecommons.org/licenses/by/4.0/info:eu-repo/semantics/openAccessoai:riunet.upv.es:10251/1884722026-06-13T07:49:27Z
score 15,300724

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