Synthesis of 6-deoxy-5-thio-D-glucose.
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-alpha-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-1,2-O-isopropylidene-beta-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-alpha-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.
Bozó
E
E
Institute for Drug Research, Budapest, Hungary.
Boros
S
S
Kuszmann
J
J
Gács-Baitz
E
E
D017607:Aluminum Compounds / Q000378:metabolism; D001894:Borohydrides / Q000378:metabolism; D003847:Deoxyglucose / Q000031:analogs & derivatives*; D004220:Disulfides / Q000138:chemical synthesis; D018020:Lithium Compounds / Q000378:metabolism; D009682:Magnetic Resonance Spectroscopy; D008698:Mesylates / Q000138:chemical synthesis; D008968:Molecular Conformation; D015394:Molecular Structure; D013438:Sulfhydryl Compounds / Q000138:chemical synthesis; D013863:Thioglucosides / Q000138:chemical synthesis*
D017607:Aluminum Compounds; D001894:Borohydrides; D004220:Disulfides; D018020:Lithium Compounds; D008698:Mesylates; D013438:Sulfhydryl Compounds; D013863:Thioglucosides; C042073:lithium aluminum hydride; C025364:sodium borohydride; D003847:Deoxyglucose