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Issue 29, 2012
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Stereospecific synthesis and catalytic activity of l-histidylidene metal complexes

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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 α-carbon. The stereospecificity of the reaction was conveniently probed by 31P 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.

Graphical abstract: Stereospecific synthesis and catalytic activity of l-histidylidene metal complexes

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Article information

13 Apr 2012
16 May 2012
First published
16 May 2012

Dalton Trans., 2012,41, 8813-8821
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Stereospecific synthesis and catalytic activity of L-histidylidene metal complexes

A. Monney, E. Alberico, Y. Ortin, H. Müller-Bunz, S. Gladiali and M. Albrecht, Dalton Trans., 2012, 41, 8813
DOI: 10.1039/C2DT30799E

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