Highly efficient production of heteroarene phosphonates by dichromatic photoredox catalysis

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 hetero...

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Autores: Díaz Díaz, David, Herrera Luna, Jorge C., Consuelo Jiménez, M., Pérez Ruiz, Raúl
Tipo de recurso: artículo
Estado:Versión publicada
Fecha de publicación:2021
País:España
Institución:Universidad de La Laguna (ULL)
Repositorio:RIULL. Repositorio Institucional de la Universidad de La Laguna
OAI Identifier:oai:riull.ull.es:915/42198
Acceso en línea:http://riull.ull.es/xmlui/handle/915/42198
Access Level:acceso abierto
Palabra clave:dichromatic photocatalysis
visible light
gel nanoreactor
heteroarene halides
phosphorylation
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spelling Highly efficient production of heteroarene phosphonates by dichromatic photoredox catalysisDíaz Díaz, DavidHerrera Luna, Jorge C.Consuelo Jiménez, M.Pérez Ruiz, Raúldichromatic photocatalysisvisible lightgel nanoreactorheteroarene halidesphosphorylationA 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,Ndiisopropylethylamine (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•− (green region). The resultant strongly reducing excited agent DCA•−* is capable of even activate five-membered heteroarene halides (Br, Cl) with high reduction potentials (∼−2.7 V) to effect the C(sp2)−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.American Chemical Society202520252021info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://riull.ull.es/xmlui/handle/915/42198reponame:RIULL. Repositorio Institucional de la Universidad de La Lagunainstname:Universidad de La Laguna (ULL)InglésApplied Materials & Interfaces;13, 2021Atribución 4.0 Internacionalhttp://creativecommons.org/licenses/by/4.0/info:eu-repo/semantics/openAccessoai:riull.ull.es:915/421982026-06-22T13:13:57Z
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
Díaz Díaz, David
dichromatic photocatalysis
visible light
gel nanoreactor
heteroarene halides
phosphorylation
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 Díaz Díaz, David
Herrera Luna, Jorge C.
Consuelo Jiménez, M.
Pérez Ruiz, Raúl
author Díaz Díaz, David
author_facet Díaz Díaz, David
Herrera Luna, Jorge C.
Consuelo Jiménez, M.
Pérez Ruiz, Raúl
author_role author
author2 Herrera Luna, Jorge C.
Consuelo Jiménez, M.
Pérez Ruiz, Raúl
author2_role author
author
author
dc.subject.none.fl_str_mv dichromatic photocatalysis
visible light
gel nanoreactor
heteroarene halides
phosphorylation
topic dichromatic photocatalysis
visible light
gel nanoreactor
heteroarene halides
phosphorylation
description 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,Ndiisopropylethylamine (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•− (green region). The resultant strongly reducing excited agent DCA•−* is capable of even activate five-membered heteroarene halides (Br, Cl) with high reduction potentials (∼−2.7 V) to effect the C(sp2)−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
2025
2025
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/publishedVersion
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv http://riull.ull.es/xmlui/handle/915/42198
url http://riull.ull.es/xmlui/handle/915/42198
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv Applied Materials & Interfaces;13, 2021
dc.rights.none.fl_str_mv Atribución 4.0 Internacional
http://creativecommons.org/licenses/by/4.0/
info:eu-repo/semantics/openAccess
rights_invalid_str_mv Atribución 4.0 Internacional
http://creativecommons.org/licenses/by/4.0/
eu_rights_str_mv openAccess
dc.publisher.none.fl_str_mv American Chemical Society
publisher.none.fl_str_mv American Chemical Society
dc.source.none.fl_str_mv reponame:RIULL. Repositorio Institucional de la Universidad de La Laguna
instname:Universidad de La Laguna (ULL)
instname_str Universidad de La Laguna (ULL)
reponame_str RIULL. Repositorio Institucional de la Universidad de La Laguna
collection RIULL. Repositorio Institucional de la Universidad de La Laguna
repository.name.fl_str_mv
repository.mail.fl_str_mv
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