EIN NEUER EFFIZIENTER WEG ZUR DARSTELLUNG VON GLYCOPYRANOSYLCYANIDEN (2,6-ANHYDROALDONONITRILES) OHNE NACHBARGRUPPENBETEILIGUNG. REDUKTION VON 2,6-ANHYDRO-1-DESOXY-1-NITROALDITOLEN MIT PHOSPHORTRICHLORID

Article abstract of DOI:10.1016/S0008-6215(00)90894-2

D-Glucose, D-mannose, and D-galactose gave in two steps the corresponding per-O-acetyl-2,6-anhydro-1-deoxy-1-nitroheptitols.Treatment with phosphorus trichloride in pyridine gave directly the corrresponding 3,4,5,7-tetra-O-acetyl-2,6-anhydroheptononitriles ("glycopyranosyl cyanides").The same treatment was applied to the 3,4,5-tri-O-acetyl-2,6-anhydro-1-deoxy-1-nitrohexitols, prepared from D-xylose, D-lyxose, L-aradinose, and D-ribose, and led to the corresponding 3,4,5-tri-O-acetyl-2,6-anhydrohexononitriles in yields ranging from 65 to 80percent.No anomerization was observed, thus allowing the preparation in high yields, of cyanides having even the 1,2-cis configuration.The anhydronitriles were compared with other known examples of this class of compounds and conformational equilibria in solution determined by 1H-n.m.r. spectroscopy.A significant anomeric effect of the cyano group is doubtful.Instead, a stabilizing effect by the 1,3-diaxial arrangement of a cyano group and an acetoxy substituent seems to be present.