Lemieux and Koto' recently published a review.on the conformational properties of glycosidic linkages, wherein 13C chemical shifts around glycosidic linkages are shown to depend upon conformations thereabout by using some cyclohexyl glucosides. hiring our studies of structural determinations and t3C FT NMR signal assignments of natural plant glyccsides, we also found that 13C signal shifts from aglycone and saccharide to glycoside, i.e., glycosidation shifts, are characteristic of chemical and steric environments of an OH group in which the glycosidation takes place, depending on the saccharide. This finding becomes important for determining the glycosidation position in an aglycone moiety and the kind(s) and sequence of sugar moiety in a natural glycoside without chemical degradation, bacause some glycosides are unstable against acid hydrolysis. We wish to report here a systematic study of the glycosidation shift using various o-and/or 8-gglucopyranosides (z-3 and their tetra-0-acetyl derivatives (&-a, which was prompted by a similar study by Tanaka and coworkers .* t3C FT NMR spectra of various alcohols and their glucosides (2-2 were determined in pyridine+, most natural glycosides being soluble in pyridine. The spectra of the alcohols and their acetates @a-2a were measured in CDCI,. 13C signals of the aglycone alcohols employed were alread?'* or easily assigned by the usual procedure;' those of the methyl glucosides were kn0wn.s TABLE 1 lists the data obtained.