Thiosugars. VII. Synthesis of 1-Thio-2-deoxy-β-D-glucose Derivatives

Abstract

1-Thio-2-deoxy-β-D-glucose sodium salt dihydrate (X), m.p. 114∼115°, [α]¹⁵_D+22°was prepared starting from 3, 4, 6-tri-O-acetyl-D-glucal (I) via 2-deoxy-3, 4, 6-tri-O-acetyl-D-glucopyranosyl bromide (VII) and 2-deoxy-3, 4, 6-tri-O-acetyl-β-D-glucopyranosyl ethylxanthate (VIII). The product afforded 2-deoxy-D-glucose anilide, benzyl 1-thio-2-deoxy-β-D-glucoside, m.p. 96∼97°, [α]²¹_D-242°, and benzyl 1-thio-2-deoxy-3, 4, 6-tri-O-acetyl-β-D-glucoside, m.p. 60∼61°, [α]¹⁶_D-192°. The optical rotatory dispersion of VIII reveals the similarity with that of 2, 3, 4, 6-tetra-O-acetyl-β-D-glucopyranosyl ethylxanthate, which supports the β-configuration of VIII, together with that of the compounds derived from VIII. Heating of I with thioacetic acid for 5.5 hours in the presence of a small amount of sulfuric acid, afforded crystals, m.p. 104∼105°, [α]²²_D+164°, in 60% yield. The structure was assigned to be 1-S-acetyl-1-thio-2, 3-didehydro-2, 3-dideoxy-4, 6-di-O-acetyl-α-D-eryhtro-hexose (II).