0000000000403170
AUTHOR
Achille Inesi
STABILITY AND ORGANOCATALYTIC EFFICIENCY OF N-HETEROCYCLIC CARBENES ELECTROGENERATED IN ORGANIC SOLVENTS FROM IMIDAZOLIUM IONIC LIQUIDS
The kinetic of degradation of 1-butyl-3-methylimidazole-2-ylidene (selected as model N-heterocyclic carbene - NHC), generated in organic solvents by cathodic reduction of the parent 1-butyl-3- methylimidazolium salts BMIm-X, was studied by a simple voltammetric analysis. The effect of NHC degradation rate on the efficiency of an organocatalyzed reaction (the synthesis of g-butyrolactone from cinnamaldehyde and trifluoromethylacetophenone) was investigated. The nature of the solvent and of the anion X have a remarkable effect on the stability of the NHC, the bis(trifluoromethylsulfonyl) imide anion being the best for a long lasting carbene (while acetonitrile seems to be the worst solvent). …
N-heterocyclic carbenes and parent cations: acidity, nucleophilicity, stability, and hydrogen bonding-Electrochemical Study and ab initio calculations
N-Heterocyclic carbenes (NHCs) are widely used as organocatalysts. Their reactivity (and instability) is related to their basicity and nucleophilicity, which, in turn, are linked to their scaffold. NHCs can be generated by chemical deprotonation or electrochemical reduction of the parent azolium cations, NHCH+s. Cyclic voltammetry enabled the reduction potential of the NHCH+s to be determined; the reduction potential is related to the acidity of the NHCH+s and the oxidation potential of the NHCs, which is related to the nucleophilicity of the NHCs. It was thus possible to order different NHCH+s and NHCs by their acidity and nucleophilicity, respectively. A study on the stability of NHCs was…
Azolium and acetate ions in DMF: Formation of free N-heterocyclic carbene. A voltammetric analysis
In order to reveal the possible formation of free N-heterocyclic carbene (NHC) in DMF-azolium and acetate solutions, the proton exchange equilibrium between azolium cations and CH3COO− was investigated (by cyclic voltammetry) by adding CH3COOH or tetrabutylammonium acetate to DMF solutions of imidazolium or thiazolium salts of different acidity.The voltammetric analysis confirms that the deprotonation of the azolium cation by CH3COO− (with the formation of free NHC) is significant in the case of the more acidic thiazolium cations, while it is not effective with the less acidic imidazolium ones.Accordingly, the NHC-catalyzed benzoin condensation was carried out in DMF solutions of azolium sa…