SYNTHESIS OF 2-(BETA-D-GLYCOPYRANOSYL)NITROETHENES AND 2-(BETA-D-GLYCOPYRANOSYL)NITROETHANES VIA ALDEHYDO DERIVATIVES

pH-Controlled ozonolysis of the sodium nitronate forms of beta-D-hexop yranosylnitromethanes (2,6-anhydro-1-deoxy-1-nitroheptitols) at room t emperature produced the corresponding 2,6-anhydroheptoses. Without iso lation, these glycosylated formaldehydes were converted by the convent ional nitromethane route to the corresponding 2-(beta-D-hexopyranosyl) nitroethenes (8a-c), via the intermediate acetylated 2-(beta-D-hexopyr anosyl)-2-hydroxynitroethanes. A spontaneous beta-elimination of the a cetoxy group vicinal to the nitro group occurred in acidic medium with the 2-acetamido-2-deoxy-beta-D-glucopyranosyl derivative, but did not occur with the parent beta-D-glucopyranosyl compound or its D-galacto or D-manno epimers. 2-C-Glycosylated nitroethenes were further transf ormed by a regioselective catalytic reduction to 2-(beta-D-hexopyranos yl)nitroethanes. (C) 1996 Elsevier Science Ltd.