Behaviour of the primary nitro group under denitration conditions

Treatment of per-O-acetylated or acetalated glycosylnitromethanes derived f rom the common hexoses and pentoses with tributyltin hydride and a catalyti c amount of a radical initiator [1,1'-azobis(cyclohexanecarbonitrile)] in r efluxing benzene easily afforded the corresponding glycosylmethanal oximes in 84-97% yields. Per-O-acetylated C-beta-glycopyranosylmethanal oximes wer e employedfor synthesis of versatile C-beta-glycopyranosyl cyanides of the beta-D-gluco, beta-D-manno, beta-D-galacto, beta-D-xylo, and beta-L-rhamno configurations.