DOI: https://doi.org/10.24820/ark.5550190.p010.034 Page 365 © ARKAT USA, Inc The Free Internet Journal for Organic Chemistry Paper Archive for Organic Chemistry Arkivoc 2017, part iv, 365-376 Highly efficient carbene and polycarbene catalysis of the transesterification reaction Konstantin A. Marichev, a Nikolai I. Korotkikh,* b Alan H. Cowley, c Vagiz Sh. Saberov, b Nataliya V. Glinyanaya, a Gennady F. Rayenko, a and Oles P. Shvaika a a The L.M. Litvinenko Institute of Physical Organic and Coal Chemistry, Ukrainian Academy of Sciences, 50 Kharkiv road, Kiev 02160, Ukraine b The Institute of Organic Chemistry, Ukrainian Academy of Sciences, 5, Murmanskaya Str., Kyiv-94, 02660, Ukraine c Department of Chemistry, The University of Texas at Austin, 1 University Station A5300, Austin, Texas 78712-0165, U.S.A. Email: nkorotkikh@ua.fm Received 01-27-2017 Accepted 03-12-2017 Published on line 06-27-2017 Abstract Highly efficient carbene and polycarbene catalysis of the transesterification reaction of ethyl benzoate in methanol has been observed and results in values of TON as high as 4000 –6150 at a molar ratio of ester to methanol of 1:18 at room temperature. The most effective catalysts were found to be the individual carbenes or in situ generated carbenes, namely adamantyl and aromatic substituted cyclic compounds and polymeric carbenes. None of the reactions requires the use of molecular sieves. The polymeric imidazol-2-ylidene catalyst was used for the efficient production of biodiesel fuel from sunflower oil. Keywords: Carbenes, transesterification, catalysis, efficiencies