Structures of Two Sulfated Unsaturated Disaccharides Isolated from Enzymatic Digests of ω-Heparin (Whale Heparin)

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Abstract
The structures of two sulfated unsaturated disaccharides, compounds 12 and 15a, isolated from eliminase [EC 4.2.2.7] digests of ω-heparin (whale heparin), were determined by enzymatic and chemical methods and by proton magnetic resonance spectral analyses. Digestion of compounds 12 and 15a with α-L-Δ4,5-iduronidase produced N-sulfated .glucosamine and N-, 6-O-disulfated glucosamine, respectively, together with sulfated a-keto acid, indicating the Δ4,5-hexosyluronic acid moiety of these compounds to be 4-deoxy-sulfoxy-α-L-threo-hex-4-enopyranosyluronic acid. Methyl di-O-methyl-N-, O-diacetylglucosaminides, prepared from hydrogen-reduced 12 and 15a by desulfation, N-acetylation, permethylation, methanolysis, andacetylation, in succession, were identified as α, β-methyl 3,6-di-O-methyl-N, 4-O-diacetylgluco-saminides by gas chromatography. This finding provided definite evidence for 1→4 Δ4,5-hexosyluronic acid linkages. In addition to the above observations, proton magnetic resonance spectral studies indicated that the structures of compounds 12 and 15a were 2-Sulfoamino-2-deoxy-4-O-(4-deoxy-2-sulfoxy-α:-L-threo-hex-4-enopyranosyluronic acid)-D-glucose and 2-sulfo-amino- 2-deoxy-6-sulfoxy-4-O-(4-deoxy-2-sulfoxy-α-L-threo-hex-4 -enopyranosyluronic acid)-D-glucose, respectively. The former compound was shown to be a novel disac-charide. The high yield of this compound suggests that it is derived from a major repeating unit of ω-heparin.

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