Carbohydr .res 1987,167,55.pdf

Carbohydrate Research, 167 (1987) 55-66 Elsevier Science Publishers B.V., Amsterdam - Printed in The Netherlands 55 SYNTHESES OF (ZNITROVINYL)AMINO SUGARS AND 2- AND 3-(AL- DITOL-l-YL)-4-NITROPYRROLES*,+ ANTONIO G~MEZ-SANCHEZ, FRANCISCO-JAVIER HIDALGO. AND Jo-Lurs CHIARA Institute a’e la Grass y sus Derivados, C.S.I.C., and Departamento de Qufmica Orghica “Profesor Garcia Gondler”, Facultad de Qulmica, Universidad de Sevilla, Apartado de Correos No. 553, 41071- Seville (Spain) (Received August lst, 1986; accepted for publication, November 8th, 1986) ABSTRACT Reactions of Zamino-2-deoxy-D-glucose and its N-butyl derivative with l- ethoxy-Znitroethene produced 2-deoxy-2-[(2-nitrovinyl)amino]-D-glucose (6) and its N-butyl derivative (8), respectively, in high yields. The spectra of these com- pounds indicated that they were cu,p-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 corre- sponding tetra-acetates 7 and 9. The reaction of P-D-glucopyranosylamine with l- ethoxy-2-nitroethene yielded syrupy l-(fl-D-glucopyranosylamino)-2-nitroethene, which was characterised as the crystalline tetra-0-acetyl derivative. Compounds 6 and 8 cyclised readily to give the 4-nitro-2-(D-arubino-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 l-ethoxy-2-nitroethene in boiling methanol. Similar reactions with l-amino-l-deoxy-D-fructose and its N-methyl, N-butyl, and N-p-tolyl derivatives afforded the respective 4-nitro-3-(D-arubino-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)nitropyrroles. INTRODUCIION l-Amino-2-nitroalkenes (“nitroenamines”) have attracted interest because of their pharmacological properties2v3 and utility