Author, as appears in the article.: Montserrat Diéguez Oscar Pàmies MARIA BIOSCA Carlota Borràs
Department: Química Física i Inorgànica
URV's Author/s: DIÉGUEZ FERNÁNDEZ, MONTSERRAT PAMIES OLLÉ, OSCAR MARIA BIOSCA BORRÀS NOGUERA, CARLOTA
Keywords: reaction intermediates asymmetric catalysis iridium
Abstract: We report a reduced but structurally valuable
phosphite/phosphinite-thioether ligand library for the Irhydrogenation
of 40 minimally functionalized alkenes,
including relevant examples with poorly coordinative groups.
We found that enantiomeric excesses are mainly dependent on
the substrate structure and on some ligand parameters (i.e., the
type of thioether/phosphorus moieties and the configuration of
the phosphite group), whereas the substituents of the biaryl
phosphite moiety had little impact. By tuning the ligand
parameters we were able to find highly selective catalysts for a
range of substrates (ee’s up to 99%). These phosphite/phosphinite-thioether ligands have a simple backbone and thus yield
simple NMR spectra that reduce signal overlap and facilitate the identification of relevant intermediates. Therefore, by combining
HP-NMR spectroscopy and theoretical studies, we were also able to identify the catalytically competent Ir-dihydride alkene
species, which made it possible to explain the enantioselectivity obtained.
Research group: Organometàl.lics i Catàlisi Homogènia
Thematic Areas: Chemistry Química Química
licence for use: https://creativecommons.org/licenses/by/3.0/es/
ISSN: 0276-7333
Author identifier: 0000-0002-8450-0656 0000-0002-2352-8508 n/a n/a
Record's date: 2015-11-18
Last page: 5334
Journal volume: 34
Papper version: info:eu-repo/semantics/acceptedVersion
Licence document URL: https://repositori.urv.cat/ca/proteccio-de-dades/
Entity: Universitat Rovira i Virgili
Journal publication year: 2015
First page: 5321
Publication Type: Post-print
Repositori URV