PHOTO-OXYGENATION OF GLYCOSYLFURANS. REARRANGEMENT OF C-GLYCOSYL INTO O-GLYCOSYL DERIVATIVES

Article abstract of DOI:10.1016/0008-6215(84)85060-0

Photo-oxygenation of 3-ethoxycarbonyl-5-(2,3-O-isopropylidene-β-D-erythrofuranosyl)-2-methylfuran and 3-hydroxymethyl-5-(2,3-O-isopropylidene-β-D-erythrofuranosyl)-2-methylfuran yields the corresponding endo-peroxydes which rearrange at room temperature into the O-glycosyl derivatives ethyl 2,3-O-isopropylidene-β-D-erythrofuranosyl 2-acetylfumarate and 2,3-O-isopropylidene-β-D-erythrofuranosyl 3-acetyl-3-hydroxymethylacrylate, respectively.The endo-peroxides can be reduced without rearrangement, yielding C-glycosyl derivatives.Alcoholysis of the O-glycosyl derivatives yields 2,3-O-isopropylidene-D-erythrose, dialkyl 2-acetyl-3-alkoxysuccinates, 4-ethoxycarbonyl-5-methoxy-5-methyl-2-oxo-2,5-dihydrofuran and 4-hydroxymethyl-5-methoxy-5-methyl-2-oxo-2,5-dihydrofuran.