Syntheses of (2-nitrovinyl)amino sugars and 2- and 3-(alditol-1-YL)-4-nitropyrroles

Abstract

Reactions of 2-amino-2-deoxy-d-glucose and its N-butyl derivative with 1-ethoxy-2-nitroethene produced 2-deoxy-2-[(2-nitrovinyl)amino]-d-glucose (6) and its N-butyl derivative (8), respectively, in high yields. The spectra of these compounds indicated that they were α,β-anomeric mixtures, and also that 6 existed as equilibrium mixtures of the Z- and E-geometrical isomers, the proportions of which depended on the polarity of the medium. Acetylation of 6 and 8 afforded the corresponding tetra-acetates 7 and 9. The reaction of β-d-glucopyranosylamine with 1-ethoxy-2-nitroethene yielded syrupy 1-(β-d-glucopyranosylamino)-2-nitroethene, which was characterised as the crystalline tetra-O-acetyl derivative. Compounds 6 and 8 cyclised readily to give the 4-nitro-2-(d-arabino-tetritol-1-yl)pyrroles 12 and 14, which could also be obtained by treatment of 2-amino-2-deoxy-d-glucose and its N-butyl derivative with 1-ethoxy-2-nitroethene in boiling methanol. Similar reactions with 1-amino-1-deoxy-d-fructose and its N-methyl, N-butyl, and N-p-tolyl derivatives afforded the respective 4-nitro-3-(d-arabino-tetritol-1-yl)pyrroles. A series of 4-nitro-3- and -2-pyrrolecarbaldehydes was obtained by periodate oxidation of the 2- and 3-(alditol-1-yl)-4-nitropyrroles.