Abstract The triad tribenzylphosphite-iodine-pyridine offers a general selective method for phosphorylation reactions of primary alcohols of unprotected α-diols and polyols. A mechanistic study by 31P NMR allowed to evidence the formation, from iododibenzyl phosphate and pyridine, of a very reactive pyridinium salt intermediate. This analysis shows that pyridine behaves as a covalent catalyst like DMAP in acylation reactions from ...