AbstractAn improved, large‐scale preparation is described, leading from 2‐acetamido‐2‐deoxy‐D‐glucose to benzyl 2‐acetamido‐4,6‐O‐benzylidene‐3‐O‐[(R)‐1‐carboxyethyl]‐2‐deoxy‐α‐D‐glucopyranoside (α‐BenzylN‐acetyl‐4,6‐O‐benzylidenemuramic acid.5r) and its (S)‐isomer (α‐BenzylN‐acetyl‐4,6‐O‐benzylideneisomuramic acid,5s)viachromatographic separation of their methyl esters (4rand4s). The high yield and complete separation of4rand4sallow a reliable assessment of the low stereoselectivity of the lactyl ether synthesis step from racemic 2‐chloropropionic acid. Similarly, syntheses employing pure enantiomers of 2‐chloropropionic acid were disclosed as not completely stereospecific. Coupli