Ritter-type reaction of C-(1-bromo-1-deoxy-D-glycopyranosyl)formamides and its application for the synthesis of oligopeptides incorporating anomeric α-amino acids

Abstract

O-Peracetylated or -perbenzoylated C-(1-bromo-1-deoxy-D-glycopyranosyl)formamides of D-gluco, D-galacto, and D-arabino configuration were reacted with Ag(I)-salts or HgO in nitrile solvents to give N-acyl-1-cyano-D-glycopyranosylamines with an axial C-N bond at the anomeric centre. In the presence of HgBr(2), Hg(CN)(2), or InCl(3) the anomer of the above glycosylamine with an equatorial C-N bond was also isolated or detected. In CH(3)NO(2) solutions as few as 5-10 equiv of the nitrile were sufficient to get acceptable yields for the products. Under similar conditions N-substituted C-(2,3,4,6-tetra-O-acetyl-1-bromo-1-deoxy-β-D-galactopyranosyl)formamides gave anomeric spiro-oxazoline derivatives which, upon mild acidic hydrolysis, opened up to di- and tripeptides of anomeric α-amino acids.