Improving Site Selectivity in Phosphorylation of Amphiphilic Diols through Catalyst Design

Organocatalysts based on a nucleophilic core, decorated with long hydrocarbon or oligoether outer-sphere tails were successfully applied for attenuating the site selectivity in phosphorylation of a model amphiphilic diol. Under the influence of the catalysts, the preference for the first functionalization of the hydroxyl at the apolar domain increased dramatically to render the ratio up to 3.9 : 1 between the monophosphorylated products, at 50 % substrate consumption (vs. 1.8 : 1 in the alike reaction without the catalyst). A considerable influence of the catalyst design, particularly the core nature and the tails structure, on the rate and the selectivity of the reaction was observed.