In order to design improved chiral ruthenium catalysts for asymmetric olefin metathesis, enantiomeric catalysts incorporating C1-symmetric N-Heterocyclic carbenes (NHC) ligands with syn-related substituents on the backbone were synthesized starting from meso-1,2-diphenylethylenediamine. The absolute configuration of the enantiomers of the desymmetrized meso diamine was assigned by optical rotation analysis and in silico calculations, and was found to be maintained in their respective ruthenium catalysts by comparison of the relative electronic circular dichroism (ECD) spectra. The catalytic behaviour of the enantiomeric ruthenium complexes was investigated in model asymmetric metathesis transformations and compared to that of analogous complexes bearing C1-symmetric NHC ligands with an anti backbone. Modest enantioselectivities were registered and different catalyst properties depending on the nature of stereochemical relationship of substituents on the backbone were observed.

Enantiopure C1-symmetric N-heterocyclic carbene ligands from desymmetrized meso-1,2-diphenylethylenediamine: application in ruthenium-catalyzed olefin metathesis / Paradiso, Veronica; Menta, Sergio; Pierini, Marco; Della Sala, Giorgio; Ciogli, Alessia; Grisi, Fabia. - In: CATALYSTS. - ISSN 2073-4344. - ELETTRONICO. - 6:11(2016). [10.3390/catal6110177]

Enantiopure C1-symmetric N-heterocyclic carbene ligands from desymmetrized meso-1,2-diphenylethylenediamine: application in ruthenium-catalyzed olefin metathesis

MENTA, SERGIO;PIERINI, MARCO;CIOGLI, Alessia;
2016

Abstract

In order to design improved chiral ruthenium catalysts for asymmetric olefin metathesis, enantiomeric catalysts incorporating C1-symmetric N-Heterocyclic carbenes (NHC) ligands with syn-related substituents on the backbone were synthesized starting from meso-1,2-diphenylethylenediamine. The absolute configuration of the enantiomers of the desymmetrized meso diamine was assigned by optical rotation analysis and in silico calculations, and was found to be maintained in their respective ruthenium catalysts by comparison of the relative electronic circular dichroism (ECD) spectra. The catalytic behaviour of the enantiomeric ruthenium complexes was investigated in model asymmetric metathesis transformations and compared to that of analogous complexes bearing C1-symmetric NHC ligands with an anti backbone. Modest enantioselectivities were registered and different catalyst properties depending on the nature of stereochemical relationship of substituents on the backbone were observed.
2016
chiral N-heterocyclic carbenes; ruthenium catalysts; asymmetric olefin metathesis; enantioselective chromatography; chiro-optical characterization
01 Pubblicazione su rivista::01a Articolo in rivista
Enantiopure C1-symmetric N-heterocyclic carbene ligands from desymmetrized meso-1,2-diphenylethylenediamine: application in ruthenium-catalyzed olefin metathesis / Paradiso, Veronica; Menta, Sergio; Pierini, Marco; Della Sala, Giorgio; Ciogli, Alessia; Grisi, Fabia. - In: CATALYSTS. - ISSN 2073-4344. - ELETTRONICO. - 6:11(2016). [10.3390/catal6110177]
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11573/908511
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