Synthesis of some derivatives of 6-amino-1,5-anhydro-6-deoxy-D-glucitol and 2-amino-1,5-anhydro-2-deoxy-D-glucitol.
6-Amino-1,5-anhydro-6-deoxy-D-glucitol (11) was prepared from 2,3,4,6-tetra-O-acetyl-alpha-D-glucopyranosyl bromide (1) in six steps. Reduction of 1 with tributyltin hydride, followed by deacetylation, monomolar tosylation, and reacetylation, afforded 2,3,4-tri-O-acetyl-1,5-anhydro-6-O-toluene-p-sulfonyl-D-glucitol (9). Alternatively, tritylation of 1,5-anhydro-D-glucitol, followed by acetylation, detritylation, and tosylation, gave 9. Mesylation gave 8. Treatment of 8 or 9 with azide anion afforded the azide 10, reduction of which with tributyltin hydride gave 11, which was mesylated or tosylated, and then deacetylated to give the 6-methane-sulfonamido or 6-toluene-p-sulfonamido derivative. Similarly, mesylation or tosylation of 3,4,6-tri-O-acetyl-2-amino-1,5-anhydro-2-deoxy-D-glucitol (20) gave the 2-methanesulfonamido or 2-toluene-p-sulfonamido derivatives. Treatment of 11 and 20 with sulfur trioxide-pyridine afforded the sulfoamino derivatives, deacetylation of which gave sugar analogs of cyclamate-like compounds.
D005944:Glucosamine / Q000031:analogs & derivatives* / Q000138:chemical synthesis; D007202:Indicators and Reagents; D009682:Magnetic Resonance Spectroscopy; D013058:Mass Spectrometry; D009904:Optical Rotation; D013329:Structure-Activity Relationship
D007202:Indicators and Reagents; C050144:6-amino-1,5-anhydro-6-deoxyglucitol; C047200:1-deoxyglucosamine; D005944:Glucosamine