Stereospecific synthesis and catalytic activity of L-histidylidene metal complexes

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Title: Stereospecific synthesis and catalytic activity of L-histidylidene metal complexes
Authors: Monney, Angèle
Alberico, Elisabetta
Ortin, Yannick
Müller-Bunz, Helge
Gladiali, Serafino
Albrecht, Martin
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Date: May-2012
Online since: 2015-05-25T10:31:01Z
Abstract: We 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.
Funding Details: European Research Council
Type of material: Journal Article
Publisher: Royal Society of Chemistry
Journal: Dalton Transactions
Volume: 41
Issue: 29
Start page: 8813
End page: 8821
Copyright (published version): 2012 The Royal Society of Chemistry
Keywords: N-heterocyclic-carbeneSolid-phase synthesisChiral ionic liquidsAsymmetric catalysisAmino-acidRhodium complexesEnantioselective catalysisHydrosilylation catalystsArtificial metalloenzymesCombinatorial libraries
DOI: 10.1039/c2dt30799e
Language: en
Status of Item: Peer reviewed
Appears in Collections:Chemistry Research Collection

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