3 research outputs found
Iridium-Catalyzed Asymmetric Hydrogenation with Simple Cyclohexane-Based P/S Ligands: <i>In Situ</i> HP-NMR and DFT Calculations for the Characterization of Reaction Intermediates
We
report a reduced but structurally valuable phosphite/phosphinite-thioether
ligand library for the Ir-hydrogenation 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
Iridium-Catalyzed Asymmetric Hydrogenation with Simple Cyclohexane-Based P/S Ligands: <i>In Situ</i> HP-NMR and DFT Calculations for the Characterization of Reaction Intermediates
We
report a reduced but structurally valuable phosphite/phosphinite-thioether
ligand library for the Ir-hydrogenation 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
Conformational Preferences of a Tropos Biphenyl Phosphinooxazoline–a Ligand with Wide Substrate Scope
Excellent
enantioselectivities are observed in palladium-catalyzed
allylic substitutions of a wide range of substrate types and nucleophiles
using a bidentate ligand composed of oxazoline and chirally flexible
biaryl phosphite elements. This unusually wide substrate scope is
shown by experimental and theoretical studies of its η<sup>3</sup>-allyl and η<sup>2</sup>-olefin complexes not to be a result
of configurational interconversion of the biaryl unit, since the ligand
in all reactions adopts an <i>S</i><sub>a</sub>,<i>S</i> configuration on coordination to palladium, but rather
the ability of the ligand to adapt the size of the substrate-binding
pocket to the reacting substrate. This ability also serves as an explanation
to its excellent performance in other types of catalytic processes