Studies of Aminosugars. XII. The Absolute Structure of Kanamycin as Determined by a Copper Complex Method

N,N′-Dimethyl-di-O-methyldeoxystreptamine has been prepared from kanamycin through the hydrolysis of the totally-methylated product of O-(3-acetamido-3-deoxy-α-d-glucopyranosyl)-N,N′-diacetyldeoxystreptamine. On the other hand, N,N′-dimethyl-4,5,6-tri-O-methyldeoxy-streptamine has been prepared by hydrolysis of the totally-methylated product of N,N′-diacetyl-deoxystreptamine. The shifts in molecular rotations of the both products have then been determined, with solutions of tetramminecopper(II) sulfate, ammoniacal cuprous chloride and Cupra B being substituted for water as the solvent. By the application of the generalizations described in the foregoing paper, it has been found that the former product includes a pair of adjacent methylamino and hydroxyl groups and that the projected angle between them is about +60°. These findings led to the conclusion that the free hydroxyl group in the former product is attached to the C-6 of deoxystreptamine, indicating that, in kanamycin, 6-amino-6-deoxy-α-d-glucosyl and 3-amino-3-deoxy-α-d-glucosyl moieties are attached to the C-4 and C-6 of deoxystreptamine respectively.