In this paper, we investigate the role of structural dynamical effects on reactivity properties of selected Michael acceptors. To this aim, quantum molecular dynamics simulations were performed. Conceptual density functional theory descriptors were then evaluated on selected snapshots, providing statistical indicators suitable to assess the discrepancies between static and dynamical approaches. The implications of these results for building a predictive model correlated to Mayr's electrophilicity index are then discussed, paving the way towards a more realistic account of experimental results.