title: Modifications at C-3 and C-4 of 2-amino-2-deoxy-D-glucose.
abstract: Modifications at C-3 and C-4 of 2-amino-2-deoxy-D-glucose have been developed. A 3,4-double bond was introduced into benzyl 2-acetamido-2-deoxy-3,4-di-O-methylsulfonyl-alpha-D-glucopyranoside by treatment with NaI and Zn. Epoxidation of the double bond with m-chloroperoxybenzoic acid gave an exo-epoxide exclusively. The stereochemistry of the epoxidation product has been confirmed by an alternative synthesis. An analysis of the 1H-n.m.r. spectra indicates that both the 3,4-unsaturated derivatives and the epoxide exist in the OH1 (D) conformation. Nucleophilic reagents (F-, I-) opened the 3,4-epoxide to give 4-substituted derivatives having the D-gulo configuration. Thus, 2-acetamido-1,3,6-tri-O-acetyl-2,4-dideoxy-4-iodo-alpha-D-gulopyranose and 2-acetamido-1,3,6-tri-O-acetyl-3,4-dideoxy-4-fluoro-alpha-D-gulopyranose have been synthesized. Reduction of the double bond in the key intermediate and deprotection gave 2-acetamido-2,3,4-trideoxy-D-glucopyranose. Some of the derivatives were active as inhibitors of growth of mouse, mammary adenocarcinoma cells in culture.
mesh_terms: D000230:Adenocarcinoma / Q000378:metabolism; D000818:Animals; D002236:Carbohydrate Conformation; D002478:Cells, Cultured; D002723:Chlorobenzoates / Q000494:pharmacology; D005459:Fluorides / Q000494:pharmacology; D005944:Glucosamine / Q000031:analogs & derivatives*; D006131:Growth Inhibitors / Q000138:chemical synthesis* / Q000494:pharmacology; D007454:Iodides / Q000494:pharmacology; D007928:Lethal Dose 50; D009682:Magnetic Resonance Spectroscopy; D008325:Mammary Neoplasms, Experimental / Q000378:metabolism; D051379:Mice; D010545:Peroxides / Q000494:pharmacology; D012974:Sodium Iodide / Q000494:pharmacology; D015032:Zinc / Q000494:pharmacology
chemical_list: D002723:Chlorobenzoates; D006131:Growth Inhibitors; D007454:Iodides; D010545:Peroxides; D012974:Sodium Iodide; C000433:3-chloroperbenzoic acid; D015032:Zinc; D005944:Glucosamine; D005459:Fluorides