Each of the chiral 1, 2-and 1, 3-diols examined was derivatized exclusively to a single diastereomeric acetal by the use of a new axially chiral reagent, 2′-methoxy-1, 1′- binaphthalene-8-carbaldehyde (MBC). The absolute configuration of the original 1, 2-and 1, 3-diols was determined by the NOE correlation between the proton signals of the reagent moiety and those of the diol moiety in the acetals.