SYNTHESIS OF 1,2,4-TRI-O-ACETYL-5-DEOXY-5-C--3-O-METHYL-α- AND -β-D-XYLOPYRANOSE, AND THEIR STRUCTURAL ANALYSIS BY 400-MHz, PROTON NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY

Article abstract of DOI:10.1016/0008-6215(83)88175-0

5-Deoxy-5-iodo-1,2-O-isopropylidene-3-O-methyl-α-D-xylofuranose, prepared quantitatively from its 5-O-p-tolylsulfonyl precursor, readily gave the 5-C-(diethoxyphosphinyl) derivative.Treatment of this compound with sodium dihydrobis(2-methoxyethoxy)aluminate, followed by hydrogen peroxide, mineral acid, and hydrogen peroxide, yielded 5-deoxy-5-C-(hydroxyphosphinyl)-3-O-methyl-α,β-D-xylopyranoses in 65percent overall yield.The structures of these sugar analogs were effectively established on the basis of the mass and 400-MHz, 1H-n.m.r. spectra of the four title compounds, derived by treatment with diazomethane and then acetic anhydride in pyridine. 5-C-<(S)-(1-Acetoxyethenyl)phosphino>-1,2,4-tri-O-acetyl-5-deoxy-3-O-methyl-β-D-xylopyranose was also isolated and characterized.