The Synthesis of Kanamycin Analogs I. α-D-Glucopyranosyl Derivatives of Deoxystreptamine

Abstract

The procedure developed in this laboratory for the synthesis of ci-D-glucopyranosides based on the reaction of dimeric tri-0-acetyl-2-deoxy-2-nitroso-a-D-glucopyranosy chloride with alcohols was employed to synthesize the three cc-D-glucopyranosyl deoxystreptamines and 4,6-di-0-a-D-glucopyranosyl deoxystreptamine. Effects of p H change on the n.m.r. spectra of kananiycins A and B and of the above synthetic compounds are interpreted in terms of a conforniational change.Le procede developpi au laboratoire pour la synthese des .*-D-glucopyranosides a partir de la reaction entre le chlorure de tri-0-acttyl-dCoxy-2 nitroso-2-r-D-glucopyranosyle dimere et les alcools, a kt6 utilise pour obtenir les trois r-D-glucopyranosyl deoxystreptamines et le di-0-r-D-glucopyranosyl-4,6-deoxystreptamine. Les effets du p H sur les spectres r.m.n. des kanamycines A et B des composes synthitiques ci dessus sont interpretes par rapport au changement conformationnel.

Semisynthetic aminoglycoside antibacterials. Part 7. Synthesis of novel hexopyranosyl and hexofuranosyl derivatives of gentamine C1 and C1a

“…Water (50 ml) containing potassium hydroxide (0.4 g) was added to the residue and the mixture was heated a t 100 "C for 72 h. The mixture was neutralized with Amberlite IRC 50 (H+) resin and the resin was eluted as described previously. The eluate was evaporated to dryness and the residue was chromatographed on silica gel (30 g) (33) 43 (4.36 g) was added. The mixture was allowed to remain under argon a t 25 "C €or 72 h. The reaction mixture was concentrated and water (200 ml) was added.…”

Recent advances in the synthesis of aminoglycoside antibiotics

“…Paromamine (17) is a constituent of kanamycin C (1 0), paromomycins (5,6), and many others. Neomine (19) is a constituent of neomycins (3,4) (14); the total yield of a-glycosides was 85% and, since (14) was a racemate, the desired 4-0-and 6-0-a-glycosyl compounds (15,16) were obtained in yields of 49 and 36%, respectively. Neomine (19) was derived from paromamine by selective tosylation of its primary hydroxyl group followed by azide displacement and catalytic reduction (Ref.…”

Synthesis and Conformational Properties of Some 2′-Unsubstituted Aminoglycoside Antibiotics

“…With both compounds however, acid-catalysed condensation with iaopropanol gave a 3:l mixture of anomers in which the axial a-glycoside predominated, precluding such participatlon. of the 13C NMR spectra of these two compounds (Table 1) and of the spectra of 4-9-a-Q-and 4-&a-&-glucopyranosylgaramines (28) and (29). …”