Analysis of the Reactivity of Z-2-Ar-1-EWG-1-Nitroethene Molecular Segment in the Hetero Diels–Alder Reaction: Experimental and MEDT Quantum Chemical Study

The relative reactivity of the nitrovinyl molecular segment characterized by the "cis" orientation of nitro group and the aryl ring was evaluated based on the experimental and Density Functional Theory quantum chemical data. It was found that, on the contrary to E-R-nitroethenes, the Z-2-Ar-1-EWG-1-nitroethene molecular segment is not planar. This fact reduces the possibility of the conjugation of π-electron systems, and as a consequence, decreases the global reactivity. Due to these conditions, the reaction of the model ethyl 4,β-dinitrocinnamate and 2-methylenecyclopentane is realized as a very difficult process; however, with full regioselectivity, it leads to the expected (4 + 2) hetero Diels-Alder cycloadduct. Bonding Evolution Theory studies show that the first new C4-C5 single bond is formed in Phase VIII by merging two <i>pseudoradical</i> centers. In turn, the second C6-O1 single bond is formed in last phase of the reaction, by the depopulation of V(C6), V(O1) and V'(O1) monosynaptic basins. According to this, the title reaction was classified as a process carried out according to a "<i>one-step two-stage</i>" mechanism.