P-Stereogenic and Non-P-Stereogenic Ir-MaxPHOX in the asymmetric hydrogenation of N-Aryl imines. Isolation and X-ray analysis of imine iridacycles

A small library of Ir-MaxPHOX catalysts has been applied to the asymmetric hydrogenation of N-aryl imines. A structure activity analysis of the three-chiral-center MaxPHOX ligand has been performed. Using complex 1b, the hydrogenation of N-aryl imines took place with up to 96% enantiomeric excess at...

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Autores: Salomó i Prat, Ernest, Rojo, Pep, Hernández Lladó, Pol, Riera i Escalé, Antoni, Verdaguer i Espaulella, Xavier
Tipo de recurso: artículo
Estado:Versión aceptada para publicación
Fecha de publicación:2018
País:España
Institución:Universidad de Barcelona
Repositorio:Dipòsit Digital de la UB
OAI Identifier:oai:diposit.ub.edu:2445/128338
Acceso en línea:https://hdl.handle.net/2445/128338
Access Level:acceso abierto
Palabra clave:Hidrogenació
Lligands
Imines
Hydrogenation
Ligands
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spelling P-Stereogenic and Non-P-Stereogenic Ir-MaxPHOX in the asymmetric hydrogenation of N-Aryl imines. Isolation and X-ray analysis of imine iridacyclesSalomó i Prat, ErnestRojo, PepHernández Lladó, PolRiera i Escalé, AntoniVerdaguer i Espaulella, XavierHidrogenacióLligandsIminesHydrogenationLigandsIminesA small library of Ir-MaxPHOX catalysts has been applied to the asymmetric hydrogenation of N-aryl imines. A structure activity analysis of the three-chiral-center MaxPHOX ligand has been performed. Using complex 1b, the hydrogenation of N-aryl imines took place with up to 96% enantiomeric excess at atmospheric pressure of hydrogen and low temperature. The impact of the stereochemical information at the phosphorus center is small with respect to the selectivity, but large with respect the catalyst activity. Non-P-stereogenic analogs of MaxPHOX were also synthesized and tested, but they provided lower selectivity. The selectivity observed could be explained by taking into account that the actual catalysts were cyclometalated imine complexes formed in situ. [IrHCl(MaxPHOX)(imine)] complexes 9 and 10 were synthesized and characterized by X-ray crystallography. These complexes, via chloride abstraction, provided the active catalytic species with the same levels of selectivity. Finally, the influence of the counterion on the catalyst performance was also studied.American Chemical Society2018info:eu-repo/semantics/articleinfo:eu-repo/semantics/acceptedVersionapplication/pdfhttps://hdl.handle.net/2445/128338Articles publicats en revistes (Química Inorgànica i Orgànica)reponame:Dipòsit Digital de la UBinstname:Universidad de BarcelonaInglésVersió postprint del document publicat a: https://doi.org/10.1021/acs.joc.8b00361Journal of Organic Chemistry, 2018, vol. 83, num. 8, p. 4618-4627https://doi.org/10.1021/acs.joc.8b00361(c) American Chemical Society , 2018info:eu-repo/semantics/openAccessoai:diposit.ub.edu:2445/1283382026-05-27T06:46:51Z
dc.title.none.fl_str_mv P-Stereogenic and Non-P-Stereogenic Ir-MaxPHOX in the asymmetric hydrogenation of N-Aryl imines. Isolation and X-ray analysis of imine iridacycles
title P-Stereogenic and Non-P-Stereogenic Ir-MaxPHOX in the asymmetric hydrogenation of N-Aryl imines. Isolation and X-ray analysis of imine iridacycles
spellingShingle P-Stereogenic and Non-P-Stereogenic Ir-MaxPHOX in the asymmetric hydrogenation of N-Aryl imines. Isolation and X-ray analysis of imine iridacycles
Salomó i Prat, Ernest
Hidrogenació
Lligands
Imines
Hydrogenation
Ligands
Imines
title_short P-Stereogenic and Non-P-Stereogenic Ir-MaxPHOX in the asymmetric hydrogenation of N-Aryl imines. Isolation and X-ray analysis of imine iridacycles
title_full P-Stereogenic and Non-P-Stereogenic Ir-MaxPHOX in the asymmetric hydrogenation of N-Aryl imines. Isolation and X-ray analysis of imine iridacycles
title_fullStr P-Stereogenic and Non-P-Stereogenic Ir-MaxPHOX in the asymmetric hydrogenation of N-Aryl imines. Isolation and X-ray analysis of imine iridacycles
title_full_unstemmed P-Stereogenic and Non-P-Stereogenic Ir-MaxPHOX in the asymmetric hydrogenation of N-Aryl imines. Isolation and X-ray analysis of imine iridacycles
title_sort P-Stereogenic and Non-P-Stereogenic Ir-MaxPHOX in the asymmetric hydrogenation of N-Aryl imines. Isolation and X-ray analysis of imine iridacycles
dc.creator.none.fl_str_mv Salomó i Prat, Ernest
Rojo, Pep
Hernández Lladó, Pol
Riera i Escalé, Antoni
Verdaguer i Espaulella, Xavier
author Salomó i Prat, Ernest
author_facet Salomó i Prat, Ernest
Rojo, Pep
Hernández Lladó, Pol
Riera i Escalé, Antoni
Verdaguer i Espaulella, Xavier
author_role author
author2 Rojo, Pep
Hernández Lladó, Pol
Riera i Escalé, Antoni
Verdaguer i Espaulella, Xavier
author2_role author
author
author
author
dc.subject.none.fl_str_mv Hidrogenació
Lligands
Imines
Hydrogenation
Ligands
Imines
topic Hidrogenació
Lligands
Imines
Hydrogenation
Ligands
Imines
description A small library of Ir-MaxPHOX catalysts has been applied to the asymmetric hydrogenation of N-aryl imines. A structure activity analysis of the three-chiral-center MaxPHOX ligand has been performed. Using complex 1b, the hydrogenation of N-aryl imines took place with up to 96% enantiomeric excess at atmospheric pressure of hydrogen and low temperature. The impact of the stereochemical information at the phosphorus center is small with respect to the selectivity, but large with respect the catalyst activity. Non-P-stereogenic analogs of MaxPHOX were also synthesized and tested, but they provided lower selectivity. The selectivity observed could be explained by taking into account that the actual catalysts were cyclometalated imine complexes formed in situ. [IrHCl(MaxPHOX)(imine)] complexes 9 and 10 were synthesized and characterized by X-ray crystallography. These complexes, via chloride abstraction, provided the active catalytic species with the same levels of selectivity. Finally, the influence of the counterion on the catalyst performance was also studied.
publishDate 2018
dc.date.none.fl_str_mv 2018
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/acceptedVersion
format article
status_str acceptedVersion
dc.identifier.none.fl_str_mv https://hdl.handle.net/2445/128338
url https://hdl.handle.net/2445/128338
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv Versió postprint del document publicat a: https://doi.org/10.1021/acs.joc.8b00361
Journal of Organic Chemistry, 2018, vol. 83, num. 8, p. 4618-4627
https://doi.org/10.1021/acs.joc.8b00361
dc.rights.none.fl_str_mv (c) American Chemical Society , 2018
info:eu-repo/semantics/openAccess
rights_invalid_str_mv (c) American Chemical Society , 2018
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 Articles publicats en revistes (Química Inorgànica i Orgànica)
reponame:Dipòsit Digital de la UB
instname:Universidad de Barcelona
instname_str Universidad de Barcelona
reponame_str Dipòsit Digital de la UB
collection Dipòsit Digital de la UB
repository.name.fl_str_mv
repository.mail.fl_str_mv
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score 15.300724

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