Synthesis of 6-deoxy-5-thio-d-glucose |
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Authors: | É va Bozó ,Sá ndor Boros,Já nos Kuszmann ,Eszter Gá cs-Baitz |
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Affiliation: | aInstitute for Drug Research, P.O. Box 82, 1325 Budapest, Hungary;bCentral Research Institute for Chemistry, Hungarian Academy of Sciences, P.O. Box 17, 1525 Budapest, Hungary |
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Abstract: | Three routes were investigated for the conversion of d-glucose into the title compound. In the first approach, reduction of the 5,6-thürane ring of 5,6-dideoxy-5,6-epithio-1,2-O-isopropylidene α-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 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-α-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. |
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Keywords: | 6-Deoxy-5-thio- font-variant: small-caps" >d-glucose Reduction of 5,6-thiirane rings with LiAIH4 Rearrangement reactions of mesylated methyl 5-thio-α- font-variant: small-caps" >d-glucopyranoside Reaction mechanism transannular participation of the sulfur atom |
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