title: Simple synthesis of conformationally fixed glycosamine analogues by beckmann rearrangement at the carbohydrate ring.
abstract: Conformationally fixed carbohydrate analogues are promising small-molecule inhibitors for hydrolases like O-GlcNAcase (OGA); however, their synthesis usually requires many steps. Herein we describe cycloadditions of dichloroketene to various glycals and subsequent Beckmann rearrangements, which offer an easy and stereoselective entry to glycosamine derivatives in good yields. The reactions are applicable for hexoses, pentoses, and disaccharides, and transformations to the corresponding imidates proceed smoothly. First biological tests reveal that such imidates indeed inhibit human OGA.
authors: Department of Chemistry, University of Potsdam, Karl-Liebknecht-Str. 24-25, 14476 Potsdam (Germany), Fax: (+49) 331-977-5056.
authors: Sumaira
authors: S
authors: Umbreen
authors: Torsten
authors: T
authors: Linker
mesh_terms: D001669:Biochemical Phenomena; D002241:Carbohydrates / Q000138:chemical synthesis* / Q000737:chemistry; D004187:Disaccharides / Q000737:chemistry*; D005944:Glucosamine / Q000138:chemical synthesis* / Q000737:chemistry; D008968:Molecular Conformation; D015394:Molecular Structure; D013237:Stereoisomerism; D001619:beta-N-Acetylhexosaminidases / Q000138:chemical synthesis* / Q000737:chemistry
chemical_list: D002241:Carbohydrates; D004187:Disaccharides; C110628:hexosaminidase C; D001619:beta-N-Acetylhexosaminidases; D005944:Glucosamine
keywords: carbohydrates; cycloaddition; enzyme inhibitors; rearrangement; selective syntheses