The asymmetric α-alkylation of enolates of chiral esters derived from 2,3:4,5-di-O-isopropylidene-β-D-fructopyranose (1) was studied. The diastereoselectivities range from 1:1 to 7:3. The absolute stereochemistry of the majorS-isomers were established by chemical correlation. The diastereoselectivities of the alkylated products were similar to those observed in the deprotonation steps. The stereochemical outcome can be interpreted by an intramolecular complexation of the lithium cation of the carbohydrate ester enolates.