Synthesis of 6-deoxy-5-thio-d-glucose

✍ Scribed by Éva Bozó; Sándor Boros; János Kuszmann; Eszter Gács-Baitz

• Publisher: Elsevier Science
• Year: 1996
• Tongue: English
• Weight: 834 KB
• Volume: 290
• Category: Article
• ISSN: 0008-6215
• DOI: 10.1016/0008-6215(96)00143-7

✦ Synopsis

Three routes were investigated for the conversion of D-glucose into the title compound. In the first approach, reduction of the 5,6-thiirane ring of 5,6-dideoxy-5,6-epithio-1,2-O-isopropylidene-t~-D-glucofuranose (17) as well as that of its 3-O-allyl derivative (13) with lithium aluminium hydride was investigated; 17 afforded the corresponding 6-deoxy derivative besides di-, tri-, and poly-mers, whereas only polymers were formed from 13. In the second approach, the oxirane ring of 3-O-allyl-5,6-anhydro-l,2-O-isopropylidene-fl-L-idofuranose was reduced by sodium borohydride and the resulting 6-deoxy derivative was converted into the 5-thiobenzoate; the corresponding hex-4-enofuranose was formed as a byproduct. In the third approach partial mesylation of methyl 5-thio-a-D-glucopyranoside was attempted, but the 6-mesylate 27 could be isolated only in modest yield (28%) together with rearranged 2,5-thioanhydromannofuranoside derivatives. The mechanism of this rearrangement is discussed in detail. The 6-mesylate 27 was converted via the 6-iodo derivative into the title compound.