DFT exploration of [3 + 2] cycloaddition reaction of 1 H -phosphorinium-3-olate and 1-methylphosphorinium-3-olate with methyl methacrylate.

A Molecular Electron Density Theory (MEDT) study of the regio- and stereoselectivity of the [3 + 2] cycloaddition (32CA) reaction of 1 H -phosphorinium-3-olate and 1-methylphosphorinium-3-olate with methyl methacrylate was carried out using the B3LYP/6-31G(d) method. In order to test the method dependence for the most favorable reaction path leading to the 1 H -substituted 6- exo cycloadduct (CA) various functionals using higher basis sets were taken into consideration in the gas phase. An analysis of the energetic parameters indicates that the reaction path leading to 6- exo CA are kinetically as well as thermodynamically favored in the gas phase, THF and ethanol. The calculated energetic parameters of the 32CA reaction of these phosphorus derivatives were compared with those of methyl acrylate and their nitrogen analogues. Investigation of the global electron density transfer at the TSs indicates that these 32CA reactions have non-polar character, while electron localisation function topological analysis of the C-C bond formation along the most favorable reaction path indicates that these 32CA reactions take place through a non-concerted two-stage one-step mechanism, via highly asynchronous TSs.