title: Synthesis of some derivatives of C-(1-deoxy-1-N-substituted-D-glucopyranosyl)formic acid (D-gluco-hept-2-ulopyranosonic acid) as potential inhibitors of glycogen phosphorylase.
abstract: Per-O-benzoylated derivatives (amide, methyl ester and glycinamide) of C-(1-azido-1-deoxy-alpha-D-glucopyranosyl)formic acid obtained by azide substitution in the corresponding C-(1-bromo-1-deoxy-beta-D-glucopyranosyl)formic acid derivatives were debenzoylated by the Zemplén-protocol. Per-O-benzoylated C-(1-azido-1-deoxy-alpha-D-glucopyranosyl)formamide was dehydrated by oxalyl chloride-DMF to give the corresponding nitrile, while from its reduction mixture obtained by Raney-nickel or sodium hydrogentelluride C-(1-amino-1-deoxy-beta-D-glucopyranosyl)formamide could be isolated. Acetylation of this amino-amide by Ac2O/Py and subsequent debenzoylation gave C-(1-acetamido-1-deoxy-beta-D-glucopyranosyl)formamide. Applying the same conditions to the crude reduction mixture allowed the alpha-anomer to be isolated as a minor component. An alternative pathway to produce the above beta-anomer appeared in the reaction of C-(1-bromo-1-deoxy-beta-D-glucopyranosyl)formamide with CH3CN in the presence of Ag2CO3 to yield 1-acetamido-2,3,4,6,-tetra-O-benzoyl-1-deoxy-beta-D-glucopyranosyl cyanide, which was hydrated, in the presence of TiCl4, to the formamide. Some of the new compounds were shown to be weak inhibitors of muscle glycogen phosphorylase b.
authors.affiliation: Department of Organic Chemistry, University of Debrecen, PO Box 20, H-4010 Debrecen, Hungary.
authors.forename: Katalin
authors.initials: K
authors.lastname: Czifrák
authors.forename: László
authors.initials: L
authors.lastname: Kovács
authors.forename: Katalin E
authors.initials: KE
authors.lastname: Kövér
authors.forename: László
authors.initials: L
authors.lastname: Somsák
mesh_terms: D004791:Enzyme Inhibitors / Q000138:chemical synthesis*; D005561:Formates / Q000737:chemistry*; D024981:Glycogen Phosphorylase / Q000037:antagonists & inhibitors*
chemical_list: D004791:Enzyme Inhibitors; D005561:Formates; C030544:formic acid; D024981:Glycogen Phosphorylase