Synthesis of 4-octuloses from a derivative of D-fructose

Article abstract of DOI:10.1080/07328309608005655

Reaction of 2,3:4,5-di-O-isopropylidene-β-D-arabino-hexos-2-ulo-2,6-pyranose (1) with (methoxycarbonylmethylene)triphenylphosphorane in either dichloromethane or methanol gave methyl (E)-2,3-dideoxy-4,5:6,7-di-O-isopropylidene-β-D-arabino-oct-2-ene-4-ulo-4, 8-pyranosonate (2) or a 1:2.3 mixture of 2 and its Z-isomer (3), respectively. Bishydroxylation of 2 with osmium tetraoxide gave a mixture of methyl 4,5:6,7-di-O-isopropylidene-β-D-glycero-D-galacto-(4) and -D-glycero-D-ido-oct-4-ulo-4,8-pyranosonate (5) which were carefully resolved by column chromatography. Compound 4 was transformed into its 2,3-di-O-methyl derivative (6) which was deacetonated to 7 and subsequently degraded to dimethyl 2,3-di-O-methyl-(+)-L-tartrate (8). On the other hand, acetonation of a mixture of 4 and 5 gave the corresponding tri-O-isopropylidene derivatives (9) and (10). Compounds 4 and 5 were reduced with LiAlH₄ to the related 4,5:6,7-di-O-isopropylidene-β-D-glycero-D-galacto-(11) and -β-D-glycero-D-ido-oct-4-ulo-4,8-pyranose (12). Treatment of 11 and 12 with acetone/PTSA/CuSO₄ only produced the acetonation at the C-2,3 positions. Finally, compounds 11 and 12 were deacetonated to the corresponding D-glycero-D-galacto-(15) and D-glycero-D-ido-oct-4-ulose (16).

Full text of DOI:10.1080/07328309608005655

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Journal of Carbohydrate Chemistry
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Synthesis of 4-Octuloses from a
Derivative of d-Fructose
Isidoro Izquierdo a & Maria T. Plaza a
a Department of Organic Chemistry , Faculty of Pharmacy University
of Granada , 18071, Granada, Spain
Published online: 22 Aug 2006.
To cite this article: Isidoro Izquierdo & Maria T. Plaza (1996) Synthesis of 4-Octuloses
from a Derivative of d-Fructose, Journal of Carbohydrate Chemistry, 15:3, 303-315, DOI:
10.1080/07328309608005655
To link to this article: http://dx.doi.org/10.1080/07328309608005655
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