Stereospecific synthesis and catalytic activity of L-histidylidene metal complexes

DC FieldValueLanguage
dc.contributor.authorMonney, Angèle-
dc.contributor.authorAlberico, Elisabetta-
dc.contributor.authorOrtin, Yannick-
dc.contributor.authorMüller-Bunz, Helge-
dc.contributor.authorGladiali, Serafino-
dc.contributor.authorAlbrecht, Martin-
dc.date.accessioned2015-05-25T10:31:01Z-
dc.date.available2015-05-25T10:31:01Z-
dc.date.copyright2012 The Royal Society of Chemistryen
dc.date.issued2012-05-
dc.identifier.citationDalton Transactionsen
dc.identifier.urihttp://hdl.handle.net/10197/6598-
dc.description.abstractWe report on the synthesis, metal coordination, and catalytic impact of histidylidene, a histidine-derived N-heterocyclic carbene (NHC) ligand. The histidinium salt 3, comprising methyl substituents at both heterocyclic nitrogens and protected at the C- and N-terminus of the amino acid, was rhodated and iridated by a transmetallation protocol using Ag2O. Ambient temperature and short reaction times were pivotal for full retention of configuration at the a-carbon. The stereospecificity of the reaction was conveniently probed by P-31 NMR spectroscopy after transmetallation with rhodium(I) and coordination of enantiopure (S)-Ph-binepine. The histidylidene rhodium complexes are highly efficient catalysts for the mild hydrosilylation of ketones. For the cationic complexes [Rh(cod)(histidylidene)(phosphine)](+), lowering the temperature shifted the rate-limiting step of the catalytic reaction to an earlier stage that is not enantioselective. Hence the asymmetric induction-which is governed by the chiral phosphine-did not improve at low temperature.en
dc.description.sponsorshipEuropean Research Councilen
dc.language.isoenen
dc.publisherRoyal Society of Chemistryen
dc.subjectN-heterocyclic-carbeneen
dc.subjectSolid-phase synthesisen
dc.subjectChiral ionic liquidsen
dc.subjectAsymmetric catalysisen
dc.subjectAmino-aciden
dc.subjectRhodium complexesen
dc.subjectEnantioselective catalysisen
dc.subjectHydrosilylation catalystsen
dc.subjectArtificial metalloenzymesen
dc.subjectCombinatorial librariesen
dc.titleStereospecific synthesis and catalytic activity of L-histidylidene metal complexesen
dc.typeJournal Articleen
dc.internal.authorcontactothermartin.albrecht@ucd.ie-
dc.statusPeer revieweden
dc.identifier.volume41en
dc.identifier.issue29en
dc.identifier.startpage8813en
dc.identifier.endpage8821en
dc.identifier.doi10.1039/c2dt30799e-
dc.neeo.contributorMonney|Angèle|aut|-
dc.neeo.contributorAlberico|Elisabetta|aut|-
dc.neeo.contributorOrtin|Yannick|aut|-
dc.neeo.contributorMüller-Bunz|Helge|aut|-
dc.neeo.contributorGladiali|Serafino|aut|-
dc.neeo.contributorAlbrecht|Martin|aut|-
dc.description.othersponsorshipSwiss National Science Foundationen
dc.internal.rmsid347882255-
dc.date.updated2015-05-12T13:43:31Z-
item.grantfulltextopen-
item.fulltextWith Fulltext-
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