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Synthesis of 1d-(1,3,5/2,4)-4-acetamido-5-amino-1,2,3-cyclohexanetriol and its incorporation into a pseudo-disaccharide

Authors
Journal
Carbohydrate Research
0008-6215
Publisher
Elsevier
Publication Date
Volume
275
Issue
1
Identifiers
DOI: 10.1016/0008-6215(95)00146-k
Keywords
  • Glycosidase Inhibitor
  • Pseudo-Aminosugar
  • Ferrier'S Carbocylization

Abstract

Abstract The synthesis of the title compound and 1 d-(1,3,5/2,4)-4-acetamido-5-amino -3-O-(β- d-glucopyranosyluronic acid)-1,2,3-cyclohexanetriol is described. Starting from methyl 2-acetamido-2-deoxy-α- d-glucopyranoside 2 l-(2,4,5/3)-4-acetamido-3-benzoyloxy-2-benzyloxy-5-hydroxycyclohexanone was prepared via a series of transformations including the regioselective ring opening of the benzylidene acetal and the mercury(II)-catalyzed carbocyclic ring closure reaction of 5-enopyranoside. Stereoselective reduction of ketone 11 with NaBH(OAc) 3 gave 1 d-(1,2,4/3,5)-2-acetamido -3-O- benzoyl-4-O- benzyl-1,3,4,5-cyclohexanetetrol (88%), which was then converted into 1 d-(1,3,5/2,4)-4-acetamido-5-azido -3-O- benzoyl-2-O- benzyl-1-O- pivaloyl-1,2,3-cyclohexanetriol through selective 5-OH protection, 1- O-mesylation, and subsequent azide displacement. Saponification and hydrogenation of this gave the title compound. Selective O-debenzoylation with 1.1 equiv of K 2CO 3 in MeOH gave 1 d-(1,3,5/2,4)-4-acetamido-5-azido -2-O- benzyl-1-O- pivaloyl-1,2,3-cyclohexanetriol (73%). Glycosylation of this compound with methyl (2,3,4- tri-O- acetyl-α- d-glucopyranosyl bromide)uronate in CH 2Cl 2, using silver triflate as the promoter, afforded 1 d-(1,3,5/2,4)-4-acetamido-5-azido -2-O- benzyl-3-O-( methyl 2,3,4-tri-O- acetyl-β- d-glucopyranosyluronate )-1-O- pivaloyl-1,2,3-cyclohexanetriol ( 20) in 79% yield. Finally, O-deacylation and subsequent hydrogenation of this compound gave the basic pseudo-disaccharide.

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