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

  1. García, J.I. 1
  2. Jiménez-Osés, G. 2
  3. Martínez-Merino, V. 3
  4. Mayoral, J.A. 1
  5. Pires, E. 1
  6. Villalba, Isabel . 1
  1. 1 Universidad de Zaragoza
    info

    Universidad de Zaragoza

    Zaragoza, España

    ROR https://ror.org/012a91z28

  2. 2 Universidad de La Rioja
    info

    Universidad de La Rioja

    Logroño, España

    ROR https://ror.org/0553yr311

  3. 3 Universidad Pública de Navarra
    info

    Universidad Pública de Navarra

    Pamplona, España

    ROR https://ror.org/02z0cah89

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Revista:
Chemistry - A European Journal

ISSN: 0947-6539

Año de publicación: 2007

Volumen: 13

Número: 14

Páginas: 4064-4073

Tipo: Artículo

DOI: 10.1002/CHEM.200601358 SCOPUS: 2-s2.0-34250370773 WoS: WOS:000246573200022 GOOGLE SCHOLAR

Otras publicaciones en: Chemistry - A European Journal

Repositorio institucional: lock_openAcceso abierto Editor

Resumen

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,.