Highly selective tail-to-tail dimerization of methyl methacrylate has been realized by an N-heterocyclic carbene catalyst, giving dimethyl 2,5-dimethyl-2-hexenedioate with an E/Z ratio of 95:5 in 86% isolated yield. The umpolung mechanism is proposed on the basis of interception of the intermediates using ESI-MS analyses and deuterium-labeling experiments.

We and others have previously reported the intermolecular umpolung reactions of Michael acceptors catalyzed by an N-heterocyclic carbene (NHC). The representative tail-to-tail dimerization of methyl methacrylate (MMA) has now been intensively investigated, leading to the following conclusions: (1) The catalysis involves the deoxy-Breslow intermediate, which is quite stable and remains active after the catalysis. (2) Addition of the intermediate to MMA and the final catalyst elimination are the rate-limiting steps. Addition of the NHC to MMA and the proton transfers are relatively very rapid. (3) The two alkenyl protons of the first MMA undergo an intermolecular transfer to C3 and C5 of the dimer. (4) The initial proton transfer is intermolecular. (5) Compared with the benzoin condensation, noticeable differences in the kinetics, reversibility, and stability of the intermediates are observed.