Biochemical Studies on Thiosugars. IV. Synthesis of 1, 6-Anhydro-1, 6-sulfide-β-D-glucopyranose (Thiolevoglucosan) and 6-Deoxy-6-mercapto-1-thio-D-glucose.

Abstract

1, 6-Anhydro-1, 6-sulfide-2, 3, 4-tri-O-acetyl-β-D-glucopyranose was synthesized by alkali-degradation and successive acetylation of 6-O-tosyl-2, 3, 4-tri-O-acetyl-β-D-glucopyranosyl ethylxanthate and 6-O-tosyl-1-deoxy-1-acethylthio-2, 3, 4-tri-O-acetyl-β-D-glucopyranose, which were prepared from 6-O-tosyl-2, 3, 4-tri-O-acetyl-α-D-glucopyranosyl bromide with potassium ethylxanthate and potassium thiolacetate respectively. On desulfurization of 1, 6-anhydro-1, 6-sulfide-2, 3, 4-tri-O-acetyl-β-D-glucopyranose with Raney nickel, 6-deoxy-1, 5-anhydro-D-sorbitol tracetate was obtained. 1, 6-Dideoxy-1, 6-diacetylthio-2, 3, 4-tri-O-acetyl-β-D-glucopyranose was prepared from 6-deoxy-6-acetylthio-2, 3, 4-tri-O-acetyl-α-D-glucopyranosyl bromide, which was synthesized from 6-deoxy-6-acetylthio-1, 2, 3, 4-tetra-O-acetyl-β-D-glucopyranose, and potassium thiolacetate. The structure was also confirmed by desulfurization with Raney nickel according to give 6-deoxy-1, 5-anhydro-D-sorbitol.