The PLE/MPEG catalyzed transesterification of the glycerol ketals rac-1a and rac-1d–f with vinyl propionate in toluene proceeded with good selectivities (E= 24–34) and gave the enantiomerically enriched S-alcohols 1a and 1d–f, and the S-esters 2a and 2d–f. High selectivities (E= 99 and E≥ 200) were observed in the transesterification of the glycerol ether rac-3 and its desoxy analog rac-5, both having a secondary hydroxy group, with PLE ...