The stereoselective acylation of meso polyol 2 by vinyl acetate (solvent and acyl donor) in the presence of porcine pancreas lipase gave the corresponding monoester 5 in good yield (76%) and high enantiomeric purity (ee > 98%). The enzymatic reaction was also highly regioselective for a primary alcohol end group, and the two unprotected secondary alcohols were not involved. Compound 5 corresponds to the C(19)-C(27) fragment of rifamycin S.