Gas-phase reduction of cyclic and acyclic α,β-unsaturated ketones by hydrogen transfer on MgO. Effect of the ketone structure

Autores
Ramos, J. J.; Diez, Veronica Karina; Ferretti, Cristián Alejandro; Torresi, Pablo Antonio; Apesteguia, Carlos Rodolfo; Di Cosimo, Juana Isabel
Año de publicación
2011
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
The gas-phase hydrogen transfer reduction (HTR) of cyclic and acyclic α,β-unsaturated ketones to the corresponding unsaturated alcohols (UOL) using 2-propanol as hydrogen donor was studied on MgO as an alternative to the less selective conventional hydrogenation using high pressure H 2. The HTR of 2-cyclohexenone and mesityl oxide were used as model reactions. The MgO activity and selectivity toward the unsaturated alcohol depended on the ketone chemical structure. Cyclic 2-cyclohexenone was in fact less reactive but more selective to UOL formation than acyclic mesityl oxide, yielding about 85% UOL (91% selectivity) at 573 K. The rigid structure of 2-cyclohexenone enforces a s-trans conformation that favors selective reduction of the CO bond and thereby enhances the UOL formation. In contrast, the less rigid structure of the acyclic ketone affords the simultaneous reduction of both unsaturated bonds, CC and CO, forming also the saturated alcohol; as a consequence, maximum UOL yields of about 45% (47% selectivity) were obtained at 573 K from HTR of mesityl oxide. The unsaturated ketone conversion pathways toward UOL and other compounds also depended on the ketone structure. UOL formed on MgO as a primary product from both reactants 2-cyclohexenone and mesityl oxide, via a cyclic six-membered intermediate according to the Meerwein-Ponndorf-Verley mechanism. However the saturated alcohol was produced by consecutive UOL reduction in 2-cyclohexenone reactions but directly from mesityl oxide reduction. Reduction of the CC bond toward the saturated ketone was negligible regardless of the reactant structure whereas competing reactions such as the CC bond shift were more likely to contribute during reduction of the acyclic reactant.
Fil: Ramos, J. J.. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera". Universidad Nacional del Litoral. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera"; Argentina
Fil: Diez, Veronica Karina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera". Universidad Nacional del Litoral. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera"; Argentina
Fil: Ferretti, Cristián Alejandro. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera". Universidad Nacional del Litoral. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera"; Argentina
Fil: Torresi, Pablo Antonio. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera". Universidad Nacional del Litoral. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera"; Argentina
Fil: Apesteguia, Carlos Rodolfo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera". Universidad Nacional del Litoral. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera"; Argentina
Fil: Di Cosimo, Juana Isabel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera". Universidad Nacional del Litoral. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera"; Argentina
Materia
Α,Β-UNSATURATED KETONE
HYDROGEN TRANSFER
MEERWEIN-PONNDORF-VERLEY MECHANISM
MGO
REDUCTION
Nivel de accesibilidad
acceso abierto
Condiciones de uso
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
Repositorio
CONICET Digital (CONICET)
Institución
Consejo Nacional de Investigaciones Científicas y Técnicas
OAI Identificador
oai:ri.conicet.gov.ar:11336/212057
Acceder
id CONICETDig_56dffdd2d6200eb4c6df140adb6d2ad1
oai_identifier_str oai:ri.conicet.gov.ar:11336/212057
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Gas-phase reduction of cyclic and acyclic α,β-unsaturated ketones by hydrogen transfer on MgO. Effect of the ketone structureRamos, J. J.Diez, Veronica KarinaFerretti, Cristián AlejandroTorresi, Pablo AntonioApesteguia, Carlos RodolfoDi Cosimo, Juana IsabelΑ,Β-UNSATURATED KETONEHYDROGEN TRANSFERMEERWEIN-PONNDORF-VERLEY MECHANISMMGOREDUCTIONhttps://purl.org/becyt/ford/2.4https://purl.org/becyt/ford/2The gas-phase hydrogen transfer reduction (HTR) of cyclic and acyclic α,β-unsaturated ketones to the corresponding unsaturated alcohols (UOL) using 2-propanol as hydrogen donor was studied on MgO as an alternative to the less selective conventional hydrogenation using high pressure H 2. The HTR of 2-cyclohexenone and mesityl oxide were used as model reactions. The MgO activity and selectivity toward the unsaturated alcohol depended on the ketone chemical structure. Cyclic 2-cyclohexenone was in fact less reactive but more selective to UOL formation than acyclic mesityl oxide, yielding about 85% UOL (91% selectivity) at 573 K. The rigid structure of 2-cyclohexenone enforces a s-trans conformation that favors selective reduction of the CO bond and thereby enhances the UOL formation. In contrast, the less rigid structure of the acyclic ketone affords the simultaneous reduction of both unsaturated bonds, CC and CO, forming also the saturated alcohol; as a consequence, maximum UOL yields of about 45% (47% selectivity) were obtained at 573 K from HTR of mesityl oxide. The unsaturated ketone conversion pathways toward UOL and other compounds also depended on the ketone structure. UOL formed on MgO as a primary product from both reactants 2-cyclohexenone and mesityl oxide, via a cyclic six-membered intermediate according to the Meerwein-Ponndorf-Verley mechanism. However the saturated alcohol was produced by consecutive UOL reduction in 2-cyclohexenone reactions but directly from mesityl oxide reduction. Reduction of the CC bond toward the saturated ketone was negligible regardless of the reactant structure whereas competing reactions such as the CC bond shift were more likely to contribute during reduction of the acyclic reactant.Fil: Ramos, J. J.. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera". Universidad Nacional del Litoral. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera"; ArgentinaFil: Diez, Veronica Karina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera". Universidad Nacional del Litoral. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera"; ArgentinaFil: Ferretti, Cristián Alejandro. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera". Universidad Nacional del Litoral. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera"; ArgentinaFil: Torresi, Pablo Antonio. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera". Universidad Nacional del Litoral. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera"; ArgentinaFil: Apesteguia, Carlos Rodolfo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera". Universidad Nacional del Litoral. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera"; ArgentinaFil: Di Cosimo, Juana Isabel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera". Universidad Nacional del Litoral. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera"; ArgentinaElsevier Science2011-08info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfapplication/pdfapplication/pdfapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/212057Ramos, J. J.; Diez, Veronica Karina; Ferretti, Cristián Alejandro; Torresi, Pablo Antonio; Apesteguia, Carlos Rodolfo; et al.; Gas-phase reduction of cyclic and acyclic α,β-unsaturated ketones by hydrogen transfer on MgO. Effect of the ketone structure; Elsevier Science; Catalysis Today; 172; 1; 8-2011; 41-470920-5861CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/https://www.sciencedirect.com/science/article/pii/S0920586111001507info:eu-repo/semantics/altIdentifier/doi/10.1016/j.cattod.2011.02.034info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-10-15T14:35:38Zoai:ri.conicet.gov.ar:11336/212057instacron:CONICETInstitucionalhttp://ri.conicet.gov.ar/Organismo científico-tecnológicoNo correspondehttp://ri.conicet.gov.ar/oai/requestdasensio@conicet.gov.ar; lcarlino@conicet.gov.arArgentinaNo correspondeNo correspondeNo correspondeopendoar:34982025-10-15 14:35:38.409CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Gas-phase reduction of cyclic and acyclic α,β-unsaturated ketones by hydrogen transfer on MgO. Effect of the ketone structure
title Gas-phase reduction of cyclic and acyclic α,β-unsaturated ketones by hydrogen transfer on MgO. Effect of the ketone structure
spellingShingle Gas-phase reduction of cyclic and acyclic α,β-unsaturated ketones by hydrogen transfer on MgO. Effect of the ketone structure
Ramos, J. J.
Α,Β-UNSATURATED KETONE
HYDROGEN TRANSFER
MEERWEIN-PONNDORF-VERLEY MECHANISM
MGO
REDUCTION
title_short Gas-phase reduction of cyclic and acyclic α,β-unsaturated ketones by hydrogen transfer on MgO. Effect of the ketone structure
title_full Gas-phase reduction of cyclic and acyclic α,β-unsaturated ketones by hydrogen transfer on MgO. Effect of the ketone structure
title_fullStr Gas-phase reduction of cyclic and acyclic α,β-unsaturated ketones by hydrogen transfer on MgO. Effect of the ketone structure
title_full_unstemmed Gas-phase reduction of cyclic and acyclic α,β-unsaturated ketones by hydrogen transfer on MgO. Effect of the ketone structure
title_sort Gas-phase reduction of cyclic and acyclic α,β-unsaturated ketones by hydrogen transfer on MgO. Effect of the ketone structure
dc.creator.none.fl_str_mv Ramos, J. J.
Diez, Veronica Karina
Ferretti, Cristián Alejandro
Torresi, Pablo Antonio
Apesteguia, Carlos Rodolfo
Di Cosimo, Juana Isabel
author Ramos, J. J.
author_facet Ramos, J. J.
Diez, Veronica Karina
Ferretti, Cristián Alejandro
Torresi, Pablo Antonio
Apesteguia, Carlos Rodolfo
Di Cosimo, Juana Isabel
author_role author
author2 Diez, Veronica Karina
Ferretti, Cristián Alejandro
Torresi, Pablo Antonio
Apesteguia, Carlos Rodolfo
Di Cosimo, Juana Isabel
author2_role author
author
author
author
author
dc.subject.none.fl_str_mv Α,Β-UNSATURATED KETONE
HYDROGEN TRANSFER
MEERWEIN-PONNDORF-VERLEY MECHANISM
MGO
REDUCTION
topic Α,Β-UNSATURATED KETONE
HYDROGEN TRANSFER
MEERWEIN-PONNDORF-VERLEY MECHANISM
MGO
REDUCTION
purl_subject.fl_str_mv https://purl.org/becyt/ford/2.4
https://purl.org/becyt/ford/2
dc.description.none.fl_txt_mv The gas-phase hydrogen transfer reduction (HTR) of cyclic and acyclic α,β-unsaturated ketones to the corresponding unsaturated alcohols (UOL) using 2-propanol as hydrogen donor was studied on MgO as an alternative to the less selective conventional hydrogenation using high pressure H 2. The HTR of 2-cyclohexenone and mesityl oxide were used as model reactions. The MgO activity and selectivity toward the unsaturated alcohol depended on the ketone chemical structure. Cyclic 2-cyclohexenone was in fact less reactive but more selective to UOL formation than acyclic mesityl oxide, yielding about 85% UOL (91% selectivity) at 573 K. The rigid structure of 2-cyclohexenone enforces a s-trans conformation that favors selective reduction of the CO bond and thereby enhances the UOL formation. In contrast, the less rigid structure of the acyclic ketone affords the simultaneous reduction of both unsaturated bonds, CC and CO, forming also the saturated alcohol; as a consequence, maximum UOL yields of about 45% (47% selectivity) were obtained at 573 K from HTR of mesityl oxide. The unsaturated ketone conversion pathways toward UOL and other compounds also depended on the ketone structure. UOL formed on MgO as a primary product from both reactants 2-cyclohexenone and mesityl oxide, via a cyclic six-membered intermediate according to the Meerwein-Ponndorf-Verley mechanism. However the saturated alcohol was produced by consecutive UOL reduction in 2-cyclohexenone reactions but directly from mesityl oxide reduction. Reduction of the CC bond toward the saturated ketone was negligible regardless of the reactant structure whereas competing reactions such as the CC bond shift were more likely to contribute during reduction of the acyclic reactant.
Fil: Ramos, J. J.. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera". Universidad Nacional del Litoral. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera"; Argentina
Fil: Diez, Veronica Karina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera". Universidad Nacional del Litoral. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera"; Argentina
Fil: Ferretti, Cristián Alejandro. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera". Universidad Nacional del Litoral. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera"; Argentina
Fil: Torresi, Pablo Antonio. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera". Universidad Nacional del Litoral. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera"; Argentina
Fil: Apesteguia, Carlos Rodolfo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera". Universidad Nacional del Litoral. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera"; Argentina
Fil: Di Cosimo, Juana Isabel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera". Universidad Nacional del Litoral. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera"; Argentina
description The gas-phase hydrogen transfer reduction (HTR) of cyclic and acyclic α,β-unsaturated ketones to the corresponding unsaturated alcohols (UOL) using 2-propanol as hydrogen donor was studied on MgO as an alternative to the less selective conventional hydrogenation using high pressure H 2. The HTR of 2-cyclohexenone and mesityl oxide were used as model reactions. The MgO activity and selectivity toward the unsaturated alcohol depended on the ketone chemical structure. Cyclic 2-cyclohexenone was in fact less reactive but more selective to UOL formation than acyclic mesityl oxide, yielding about 85% UOL (91% selectivity) at 573 K. The rigid structure of 2-cyclohexenone enforces a s-trans conformation that favors selective reduction of the CO bond and thereby enhances the UOL formation. In contrast, the less rigid structure of the acyclic ketone affords the simultaneous reduction of both unsaturated bonds, CC and CO, forming also the saturated alcohol; as a consequence, maximum UOL yields of about 45% (47% selectivity) were obtained at 573 K from HTR of mesityl oxide. The unsaturated ketone conversion pathways toward UOL and other compounds also depended on the ketone structure. UOL formed on MgO as a primary product from both reactants 2-cyclohexenone and mesityl oxide, via a cyclic six-membered intermediate according to the Meerwein-Ponndorf-Verley mechanism. However the saturated alcohol was produced by consecutive UOL reduction in 2-cyclohexenone reactions but directly from mesityl oxide reduction. Reduction of the CC bond toward the saturated ketone was negligible regardless of the reactant structure whereas competing reactions such as the CC bond shift were more likely to contribute during reduction of the acyclic reactant.
publishDate 2011
dc.date.none.fl_str_mv 2011-08
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/publishedVersion
http://purl.org/coar/resource_type/c_6501
info:ar-repo/semantics/articulo
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/11336/212057
Ramos, J. J.; Diez, Veronica Karina; Ferretti, Cristián Alejandro; Torresi, Pablo Antonio; Apesteguia, Carlos Rodolfo; et al.; Gas-phase reduction of cyclic and acyclic α,β-unsaturated ketones by hydrogen transfer on MgO. Effect of the ketone structure; Elsevier Science; Catalysis Today; 172; 1; 8-2011; 41-47
0920-5861
CONICET Digital
CONICET
url http://hdl.handle.net/11336/212057
identifier_str_mv Ramos, J. J.; Diez, Veronica Karina; Ferretti, Cristián Alejandro; Torresi, Pablo Antonio; Apesteguia, Carlos Rodolfo; et al.; Gas-phase reduction of cyclic and acyclic α,β-unsaturated ketones by hydrogen transfer on MgO. Effect of the ketone structure; Elsevier Science; Catalysis Today; 172; 1; 8-2011; 41-47
0920-5861
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/url/https://www.sciencedirect.com/science/article/pii/S0920586111001507
info:eu-repo/semantics/altIdentifier/doi/10.1016/j.cattod.2011.02.034
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
eu_rights_str_mv openAccess
rights_invalid_str_mv https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
dc.format.none.fl_str_mv application/pdf
application/pdf
application/pdf
application/pdf
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dc.publisher.none.fl_str_mv Elsevier Science
publisher.none.fl_str_mv Elsevier Science
dc.source.none.fl_str_mv reponame:CONICET Digital (CONICET)
instname:Consejo Nacional de Investigaciones Científicas y Técnicas
reponame_str CONICET Digital (CONICET)
collection CONICET Digital (CONICET)
instname_str Consejo Nacional de Investigaciones Científicas y Técnicas
repository.name.fl_str_mv CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicas
repository.mail.fl_str_mv dasensio@conicet.gov.ar; lcarlino@conicet.gov.ar
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score 13.22299

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