DFT study of the selectivity of anomers in the Hilbert-Johnson reaction

The selectivity of α- and β-anomer in the Hilbert-Johnson reaction was studied by means of density functional theory (DFT) method. A new possible reaction pathway is proposed. The calculations further indicate that the proposed pathway is more preferable than the other two typical ones. In addition, quantum mechanical calculations were employed to study the solvent effect on the stability of the intermediates and the ratio of the diastereomers, which could be used to predict the ratio of two anomers expected from the proposed pathway. Furthermore, the experimentally determined products' ratio was compared to theoretical predictions and the experimental results are in good accordance with the predicted outcomes.