• Bottlenecks in the prediction of regioselectivity of [4 + 2] cycloaddition reactions: An assessment of reactivity descriptors

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    • Keywords


      Prediction of regioselectivity; [4 + 2] cycloaddition reactions; reactivity descriptors; DFT-based descriptors

    • Abstract


      B3LYP/6-31G(d) calculations were performed to obtain all the transition states and products for the 128 distinct reaction channels of Diels-Alder reactions by taking all possible combinations from a series of dienes (1N-a, 1N-b, 2N, 1P-a, 1P-b, 2P, 1O, 1S) and dienophiles (NE, PE, OE, SE, AE, OHE, MeE, CNE). The predictive ability of the values to gauge the regioselectivity of the putative [4 + 2] cycloaddition reactions is analysed. No correlation is obtained between the reaction energies and activation energies. The extent of asynchronicity is measured based on the bond order analysis. DFT-based descriptors such as the local softness (sk+ andsk), Fukui function indices (fk+ andfk), global electrophilicity index (Ω) and local electrophilicity index (Ωk) were found to be better than the conventional FMO predictions.

    • Author Affiliations


      G Gayatri1 G Narahari Sastry1

      1. Molecular Modeling Group, Organic Chemical Sciences, Indian Institute of Chemical Technology, Hyderabad - 500 007, India
    • Dates

  • Journal of Chemical Sciences | News

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