A New Insight into the Molecular Mechanism of the Reaction between 2-Methoxyfuran and Ethyl (Z)-3-phenyl-2-nitroprop-2-enoate: An Molecular Electron Density Theory (MEDT) Computational Study

The molecular mechanism of the reaction between 2-methoxyfuran and ethyl (<i>Z</i>)-3-phenyl-2-nitroprop-2-enoate was investigated using wb97xd/6-311+G(d,p)(PCM) quantum chemical calculations. It was found that the most probable reaction mechanism is fundamentally different from what was previously postulated. In particular, six possible zwitterionic intermediates were detected on the reaction pathway. Their formation is determined by the nature of local nucleophile/electrophile interactions. Additionally, the channel involving the formation of the <i>exo</i>-nitro Diels-Alder cycloadduct was completely ruled out. Finally, the electronic nature of the five- and six-membered nitronates as potential TACs was evaluated.