Theoretical study of the 1,3-DC reaction between fluorinated alkynes and azides: Reactivity indices, transition structures, IGM and ELF analysis

Abstract

DFT/B3LYP/6–31 + g(d,p) calculations were performed and reactivity indices, transition structures theory were applied to elucidate the molecular mechanism of the reaction between fluorinated alkynes and different azides. The process of cycloaddition operates through a one-step mechanism and an asynchronous transition states. Examination of the energy profile in the gas phase show two possible 1,4 and 1,5 addition channels for amid, the former is preferred. Furthermore, the Parr functions have used to elucidate the reaction's regioselectivity. It was noted that the addition of solvent (DMSO) does not affect the regioselectivity of the reactions. Analysis of charge transfer in the transition structures shows a moderate polar character for the majority of the studied reactions. Moreover, the independent gradient model based on promolecular density (IGM) has been used to evaluate the asynchronicity of the formation of the two new sigma bonds. Finally, the ELF calculation has been performed to clearly describe the formation of the previous bonds along the IRC path.