The rotamer population around the C5-C6 bond of chiral and nonchiral alkyl PD- glucopyranoside derivatives proved to be dependent on the structure of the aglycon; the population of the gg and gt rotamers decreased and increased, respectively, as the pKa of the aglycon increased, whereas the tg population remained almost constant. In addition, the rotamer populations correlate with the absolute configuration of the aglyconic carbons, ...