A molecular electron density theory study of asymmetric Diels-Alder [4 + 2] reaction's mechanism of furan with three substituted alkynes (5-R substituted-3-(3-(phenylsulfonyl)-propioloyl)-oxazolidin-2-one).

CONTEXT

The [4 +2 ] cycloaddition reactions between furan and three substituted alkynes (5-R-substituted-3-(3-(phenylsulfonyl)-propioloyl)-oxazolidin-2-one) have been investigated using the MEDT approach. Reactivity indices, reaction pathways, and activation energies are calculated. In an investigation of conceptual DFT indices, furan acts as a nucleophile, while the three substituted alkynes (5-R-substituted-3-(3-(phenylsulfonyl)-propioloyl)-oxazolidin-2-one) function as electrophiles in this reaction. The cycloaddition is regioiselective, as demonstrated by the activation and reaction energies, in clear agreement with the experiment's results. Hetero Diels-Alder [4 + 2] cycloadditions occur following a non-concerted two stages one-step molecular mechanism.

METHODS

For the purpose of this study, all calculations were performed using the Gaussian 09 software. Optimization was achieved through Berny's computational gradient optimization method, employing the B3LYP functional and the 6-31G(d) basis set. Analysis of both local and global reactivity indices provided insights into the reactivity tendencies of the reactants, distinguishing between electrophilic and nucleophilic characteristics via Parr functions. Frequency calculations were employed to identify and characterize stationary points, with transition states indicated by a single imaginary frequency and positive values of all frequencies for reactants and product. The electron localization function (ELF) was investigated using the Multiwfn software within the context of topological analyses.