QM/MM modeling of enantioselective pybox-ruthenium- and box-copper-catalyzed cyclopropanation reactions: Scope, performance, and applications to ligand design

An extensive comparison of full-QM (B3LYP) and QM/MM (B3LYP:UFF) levels of theory has been made for two enantioselective catalytic systems, namely, Pybox-Ru and Box-Cu complexes, in the cyclopropanation of alkenes (ethylene and styrene) with methyl diazoacetate. The geometries of the key reaction in...

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Autores: García, J.I. [0000-0003-1199-2087], Jiménez-Osés, G. [0000-0003-0105-4337], Martínez-Merino, V. [0000-0002-1873-0699], Mayoral, J.A., Pires, E. [0000-0002-2676-8814], Villalba, Isabel .
Tipo de recurso: artículo
Estado:Versión publicada
Fecha de publicación:2007
País:España
Institución:Universidad de La Rioja (UR)
Repositorio:RIUR. Repositorio Institucional de la Universidad de La Rioja
OAI Identifier:oai:portal.dialnet.es:doc/5bbc681fb750603269e802fc
Acceso en línea:https://investigacion.unirioja.es/documentos/5bbc681fb750603269e802fc
Access Level:acceso abierto
Palabra clave:Asymmetric catalysis
Copper
Density functional calculations
N ligands
Ruthenium
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spelling QM/MM modeling of enantioselective pybox-ruthenium- and box-copper-catalyzed cyclopropanation reactions: Scope, performance, and applications to ligand designGarcía, J.I. [0000-0003-1199-2087]Jiménez-Osés, G. [0000-0003-0105-4337]Martínez-Merino, V. [0000-0002-1873-0699]Mayoral, J.A.Pires, E. [0000-0002-2676-8814]Villalba, Isabel .Asymmetric catalysisCopperDensity functional calculationsN ligandsRutheniumAn extensive comparison of full-QM (B3LYP) and QM/MM (B3LYP:UFF) levels of theory has been made for two enantioselective catalytic systems, namely, Pybox-Ru and Box-Cu complexes, in the cyclopropanation of alkenes (ethylene and styrene) with methyl diazoacetate. The geometries of the key reaction intermediates and transition structures calculated at the QM/MM level are generally in satisfactory agreement with fullQM calculated geometries. More importantly, the relative energies calculated at the QM/MM level are in good agreement with those calculated at the full-QM level in all cases. Furthermore, the QM/MM energies are often in better agreement with the stereoselectivity experimentally observed, and this suggests that QM/MM calculations can be superior to full-QM calculations when subtle differences in inter- and intramolecular interactions are important in determining the selectivity, as is the case in enantioselective catalysis. The predictive value of the model presented is validated by the explanation of the unusual enantioselectivity behavior exhibited by a new bis-oxazoline ligand, the stereogenic centers of which are quaternary carbon atoms. © 2007 Wilcy-VCH Verlag GmbH & Co. KGaA,.2007info:eu-repo/semantics/articleSubtype: Articleinfo:eu-repo/semantics/publishedVersionapplication/pdfhttps://investigacion.unirioja.es/documentos/5bbc681fb750603269e802fcreponame:RIUR. Repositorio Institucional de la Universidad de La Riojainstname:Universidad de La Rioja (UR)Inglésinfo:eu-repo/semantics/altIdentifier/doi/10.1002/CHEM.200601358info:eu-repo/semantics/altIdentifier/wos/WOS:000246573200022info:eu-repo/semantics/altIdentifier/pissn/0947-6539QM/MM modeling of enantioselective pybox-ruthenium- and box-copper-catalyzed cyclopropanation reactions: Scope, performance, and applications to ligand design, 2007, vol. 13, núm. 14, pág. 4064-4073info:eu-repo/semantics/openAccessoai:portal.dialnet.es:doc/5bbc681fb750603269e802fc2026-06-14T12:47:17Z
dc.title.none.fl_str_mv QM/MM modeling of enantioselective pybox-ruthenium- and box-copper-catalyzed cyclopropanation reactions: Scope, performance, and applications to ligand design
title QM/MM modeling of enantioselective pybox-ruthenium- and box-copper-catalyzed cyclopropanation reactions: Scope, performance, and applications to ligand design
spellingShingle QM/MM modeling of enantioselective pybox-ruthenium- and box-copper-catalyzed cyclopropanation reactions: Scope, performance, and applications to ligand design
García, J.I. [0000-0003-1199-2087]
Asymmetric catalysis
Copper
Density functional calculations
N ligands
Ruthenium
title_short QM/MM modeling of enantioselective pybox-ruthenium- and box-copper-catalyzed cyclopropanation reactions: Scope, performance, and applications to ligand design
title_full QM/MM modeling of enantioselective pybox-ruthenium- and box-copper-catalyzed cyclopropanation reactions: Scope, performance, and applications to ligand design
title_fullStr QM/MM modeling of enantioselective pybox-ruthenium- and box-copper-catalyzed cyclopropanation reactions: Scope, performance, and applications to ligand design
title_full_unstemmed QM/MM modeling of enantioselective pybox-ruthenium- and box-copper-catalyzed cyclopropanation reactions: Scope, performance, and applications to ligand design
title_sort QM/MM modeling of enantioselective pybox-ruthenium- and box-copper-catalyzed cyclopropanation reactions: Scope, performance, and applications to ligand design
dc.creator.none.fl_str_mv García, J.I. [0000-0003-1199-2087]
Jiménez-Osés, G. [0000-0003-0105-4337]
Martínez-Merino, V. [0000-0002-1873-0699]
Mayoral, J.A.
Pires, E. [0000-0002-2676-8814]
Villalba, Isabel .
author García, J.I. [0000-0003-1199-2087]
author_facet García, J.I. [0000-0003-1199-2087]
Jiménez-Osés, G. [0000-0003-0105-4337]
Martínez-Merino, V. [0000-0002-1873-0699]
Mayoral, J.A.
Pires, E. [0000-0002-2676-8814]
Villalba, Isabel .
author_role author
author2 Jiménez-Osés, G. [0000-0003-0105-4337]
Martínez-Merino, V. [0000-0002-1873-0699]
Mayoral, J.A.
Pires, E. [0000-0002-2676-8814]
Villalba, Isabel .
author2_role author
author
author
author
author
dc.subject.none.fl_str_mv Asymmetric catalysis
Copper
Density functional calculations
N ligands
Ruthenium
topic Asymmetric catalysis
Copper
Density functional calculations
N ligands
Ruthenium
description An extensive comparison of full-QM (B3LYP) and QM/MM (B3LYP:UFF) levels of theory has been made for two enantioselective catalytic systems, namely, Pybox-Ru and Box-Cu complexes, in the cyclopropanation of alkenes (ethylene and styrene) with methyl diazoacetate. The geometries of the key reaction intermediates and transition structures calculated at the QM/MM level are generally in satisfactory agreement with fullQM calculated geometries. More importantly, the relative energies calculated at the QM/MM level are in good agreement with those calculated at the full-QM level in all cases. Furthermore, the QM/MM energies are often in better agreement with the stereoselectivity experimentally observed, and this suggests that QM/MM calculations can be superior to full-QM calculations when subtle differences in inter- and intramolecular interactions are important in determining the selectivity, as is the case in enantioselective catalysis. The predictive value of the model presented is validated by the explanation of the unusual enantioselectivity behavior exhibited by a new bis-oxazoline ligand, the stereogenic centers of which are quaternary carbon atoms. © 2007 Wilcy-VCH Verlag GmbH & Co. KGaA,.
publishDate 2007
dc.date.none.fl_str_mv 2007
dc.type.none.fl_str_mv info:eu-repo/semantics/article
Subtype: Article
info:eu-repo/semantics/publishedVersion
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv https://investigacion.unirioja.es/documentos/5bbc681fb750603269e802fc
url https://investigacion.unirioja.es/documentos/5bbc681fb750603269e802fc
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/doi/10.1002/CHEM.200601358
info:eu-repo/semantics/altIdentifier/wos/WOS:000246573200022
info:eu-repo/semantics/altIdentifier/pissn/0947-6539
QM/MM modeling of enantioselective pybox-ruthenium- and box-copper-catalyzed cyclopropanation reactions: Scope, performance, and applications to ligand design, 2007, vol. 13, núm. 14, pág. 4064-4073
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv application/pdf
dc.source.none.fl_str_mv reponame:RIUR. Repositorio Institucional de la Universidad de La Rioja
instname:Universidad de La Rioja (UR)
instname_str Universidad de La Rioja (UR)
reponame_str RIUR. Repositorio Institucional de la Universidad de La Rioja
collection RIUR. Repositorio Institucional de la Universidad de La Rioja
repository.name.fl_str_mv
repository.mail.fl_str_mv
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