A synthetic and structural study of some glycosylamines and related compounds

Abstract

A synthetic route of possible general applicability for the preparation of N-glycosylated β-aminothiols was explored. Treatment of 2-(D-gluco-1,2,3,4,5-pentahydroxypentyl)-benzthiazoline with mercury (II) acetate gives di-(N-D-glucofuranosyl-o-amino-benzenethiol)-mercury (II). Acetylation of this chelate gives the tetra-O-acetate which on removal of the mercury gives di-(N-2,3,5,6-tetra-O-acetyl-D-glucofuranosyl-o-aminophenyl)-disulphide and N-(2,3,5,6-tetra-O-acetyl-D-glucofuranosyl)-o-aminobenzenethiol under oxidizing and non-oxidizing conditions, respectively. The mercaptofuranosylamine was then converted to the S-acetyl and N,S-diacetyl derivatives. The rearrangements of the above benzthiazoline and 2-(D-gluco-1,2,3,4,5-pentahydroxypentyl)-thiazolidine-4-carboxylic acid with nickel (II) acetate were briefly investigated. The possibility of synthesizing 1-N-glycosylated-cystinyl peptides by use of the metal ion induced rearrangement of thiazol-idines is proposed. Attempted synthesis of N-glycosylated β-aminothiols by condensation of S-benzyl-L-cysteine with D-glucose or by rearrangement of o-aminophenyl 1-thio-β-D-glucopyranoside failed to give the desired products.