Investigation of a carben-catalyzed redoxreaction – running

The aim of the project is to investigate a possible extension of the use of carbenes in the filed of organocatalysis. We have recently published that due to their NHC content certain ionic liquids (such as ethyl-methylimidazolium-acetate) act as organocatalysers in the benzoin condensation1 . During this work it turned out that several other reactions – starting from the same substrate - could be catalysed (the carbene acting as a domino organocatalyst) in the same system in the presence of air. By the reproduction of these reactions we have several problems, we can reproduct neither reactions of other groups nor our reactions. This system is quite complex to examine by quantumchemistry calculations so we choose a good defined test reaction2, a carbene-catalyzed monoacylation of 1,4-Naphthoquinones with acetaldehyds. Our earlier calculations showed that3 one of the three possible initial complexes (Breslow-intermediate, Berkessel-intermediate and initial adduct) has an important role in this monoacylation reaction. The aim of this work is to calculate the reaction above with other methods and to investigate, which initial complex has role in other oxidation reactions.

1 Zs. Kelemen O. Hollóczki, J. Nagy, L. Nyulászi Organic and Biomolecular Chemistry, 2011, 9, 5362
2 M. T.Molina, C. Navarro, A. Moreno, A. G. Csaky, J. Org. Chem., 2009, 74, 9573–9575 9573
3 Investigation of a Carbene-catalyzed hidridtransfer reaction Master Thesis 2012 Zs. Kelemen, supervisor: L. Nyulászi

Project owner:
Kelemen Zsolt (Szervetlen és Analitikai Kémia Tanszék)
Szervetlen és Analitikai Kémia Tanszék (VBK-IAACHEM)