Catalytic activity of copper-bis(oxazoline) grafted on mesoporous silica in enantioselective cyclopropanation

Chiral phenyl substituted bis(oxazoline) (PhBox) was covalently immobilized through carbamate linkers onto mesoporous silica materials. These supports were previously prepared by the sol–gel method and they exhibit different textural properties. The presence and the integrity of the bis(oxazoline) l...

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Autores: Fakhfakh, Fatma, Baraket, Leila, Ghorbel, Abdelhamid, Fraile, José M., Mayoral, José A.
Tipo de recurso: artículo
Estado:Versión aceptada para publicación
Fecha de publicación:2015
País:España
Institución:Consejo Superior de Investigaciones Científicas (CSIC)
Repositorio:DIGITAL.CSIC. Repositorio Institucional del CSIC
OAI Identifier:oai:digital.csic.es:10261/154630
Acceso en línea:http://hdl.handle.net/10261/154630
Access Level:acceso abierto
Palabra clave:Bis(oxazolines)
Immobilized catalysts
Cyclopropanation
Mesoporous materials
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spelling Catalytic activity of copper-bis(oxazoline) grafted on mesoporous silica in enantioselective cyclopropanationFakhfakh, FatmaBaraket, LeilaGhorbel, AbdelhamidFraile, José M.Mayoral, José A.Bis(oxazolines)Immobilized catalystsCyclopropanationMesoporous materialsChiral phenyl substituted bis(oxazoline) (PhBox) was covalently immobilized through carbamate linkers onto mesoporous silica materials. These supports were previously prepared by the sol–gel method and they exhibit different textural properties. The presence and the integrity of the bis(oxazoline) ligand was checked by <sup>13</sup>C-CP-MAS-NMR. These chiral mesoporous materials were complexed with copper(II) triflate. In spite of the different textural properties of these supports, the copper loading, determined by ICP-AES, was nearly the same (0.041–0.044 mmol Cu/g of solid). The supported Cu(II) complexes were tested as catalysts in the enantioselective cyclopropanation of styrene with ethyl diazoacetate. Enantioselectivities are consistently lower than those obtained in homogeneous phase. Different analyses point to a difficulty in the formation of the expected chelate, due to the presence of a coordinating functional group in the linker, as responsible for the loss in enantioselectivity. The textural properties of the materials do significantly affect the behavior upon recovery.This work was made possible by the generous financial support from the Spanish Ministerio de Economía y Competitividad (Project CTQ2011-28124), the Diputación General de Aragón (E11 Group co-financed by the European Regional Development Funds) and the AECI (Agencia Española de Cooperación International project A/8491/07).Peer ReviewedSpringer NatureMinisterio de Economía y Competitividad (España)Diputación General de AragónEuropean CommissionMinisterio de Asuntos Exteriores y Cooperación (España)Consejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]2017201720152017info:eu-repo/semantics/articlehttp://purl.org/coar/resource_type/c_6501Postprintinfo:eu-repo/semantics/acceptedVersionhttp://hdl.handle.net/10261/154630reponame:DIGITAL.CSIC. Repositorio Institucional del CSICinstname:Consejo Superior de Investigaciones Científicas (CSIC)Ingléshttps://doi.org/10.1007/s11144-015-0872-xSíinfo:eu-repo/semantics/openAccessoai:digital.csic.es:10261/1546302026-05-22T06:33:51Z
dc.title.none.fl_str_mv Catalytic activity of copper-bis(oxazoline) grafted on mesoporous silica in enantioselective cyclopropanation
title Catalytic activity of copper-bis(oxazoline) grafted on mesoporous silica in enantioselective cyclopropanation
spellingShingle Catalytic activity of copper-bis(oxazoline) grafted on mesoporous silica in enantioselective cyclopropanation
Fakhfakh, Fatma
Bis(oxazolines)
Immobilized catalysts
Cyclopropanation
Mesoporous materials
title_short Catalytic activity of copper-bis(oxazoline) grafted on mesoporous silica in enantioselective cyclopropanation
title_full Catalytic activity of copper-bis(oxazoline) grafted on mesoporous silica in enantioselective cyclopropanation
title_fullStr Catalytic activity of copper-bis(oxazoline) grafted on mesoporous silica in enantioselective cyclopropanation
title_full_unstemmed Catalytic activity of copper-bis(oxazoline) grafted on mesoporous silica in enantioselective cyclopropanation
title_sort Catalytic activity of copper-bis(oxazoline) grafted on mesoporous silica in enantioselective cyclopropanation
dc.creator.none.fl_str_mv Fakhfakh, Fatma
Baraket, Leila
Ghorbel, Abdelhamid
Fraile, José M.
Mayoral, José A.
author Fakhfakh, Fatma
author_facet Fakhfakh, Fatma
Baraket, Leila
Ghorbel, Abdelhamid
Fraile, José M.
Mayoral, José A.
author_role author
author2 Baraket, Leila
Ghorbel, Abdelhamid
Fraile, José M.
Mayoral, José A.
author2_role author
author
author
author
dc.contributor.none.fl_str_mv Ministerio de Economía y Competitividad (España)
Diputación General de Aragón
European Commission
Ministerio de Asuntos Exteriores y Cooperación (España)
Consejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]
dc.subject.none.fl_str_mv Bis(oxazolines)
Immobilized catalysts
Cyclopropanation
Mesoporous materials
topic Bis(oxazolines)
Immobilized catalysts
Cyclopropanation
Mesoporous materials
description Chiral phenyl substituted bis(oxazoline) (PhBox) was covalently immobilized through carbamate linkers onto mesoporous silica materials. These supports were previously prepared by the sol–gel method and they exhibit different textural properties. The presence and the integrity of the bis(oxazoline) ligand was checked by <sup>13</sup>C-CP-MAS-NMR. These chiral mesoporous materials were complexed with copper(II) triflate. In spite of the different textural properties of these supports, the copper loading, determined by ICP-AES, was nearly the same (0.041–0.044 mmol Cu/g of solid). The supported Cu(II) complexes were tested as catalysts in the enantioselective cyclopropanation of styrene with ethyl diazoacetate. Enantioselectivities are consistently lower than those obtained in homogeneous phase. Different analyses point to a difficulty in the formation of the expected chelate, due to the presence of a coordinating functional group in the linker, as responsible for the loss in enantioselectivity. The textural properties of the materials do significantly affect the behavior upon recovery.
publishDate 2015
dc.date.none.fl_str_mv 2015
2017
2017
2017
dc.type.none.fl_str_mv info:eu-repo/semantics/article
http://purl.org/coar/resource_type/c_6501
Postprint
info:eu-repo/semantics/acceptedVersion
format article
status_str acceptedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/10261/154630
url http://hdl.handle.net/10261/154630
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv https://doi.org/10.1007/s11144-015-0872-x
Sí
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
eu_rights_str_mv openAccess
dc.publisher.none.fl_str_mv Springer Nature
publisher.none.fl_str_mv Springer Nature
dc.source.none.fl_str_mv reponame:DIGITAL.CSIC. Repositorio Institucional del CSIC
instname:Consejo Superior de Investigaciones Científicas (CSIC)
instname_str Consejo Superior de Investigaciones Científicas (CSIC)
reponame_str DIGITAL.CSIC. Repositorio Institucional del CSIC
collection DIGITAL.CSIC. Repositorio Institucional del CSIC
repository.name.fl_str_mv
repository.mail.fl_str_mv
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