SYNTHESIS OF SOME ARYL 2,3,4,6-TETRA-O-ACETYL-L-IDOPYRANOSIDES AND OF 4-METHYLCOUMARIN-7-YL α-L-IDOPYRANOSIDURONIC ACID

Article abstract of DOI:10.1016/0008-6215(83)88356-6

Several routes for synthesis of 3,5,6-tri-O-acetyl-1,2-O-isopropylidene-β-L-idofuranose have been evaluated.Previously described routes, which involved selective sulphonylation, were not reproducible on a 100-g scale.To overcome this difficulty, a new variation was developed, involving complete tosylation of 1,2-O-isopropylidene-α-D-glucofuranurono-6,3-lactone followed by reduction and acetylation.The idofuranose derivative was converted into the desired 1,2,3,4,6-penta-O-acetyl-α-L-idopyranose via 1,6-anhydro-β-L-idopyranose.Fusion of 1,2,3,4,6-penta-O-acetyl-α-L-idopyranose with 4-nitrophenol, 1- or 2-naphtol, or 4-methylcoumarin-7-ol, using freshly fused zinc chloride as catalyst, gave an anomeric mixture of glycosides, with the α anomer being preponderant.The major 4-methylcoumarin-7-yl glycoside was deacylated and converted, by catalytic oxidation, into 4-methylcoumarin-7-yl α-L-idopyranosiduronic acid, fluorogenic substrate for α-L-iduronidase.