Stereoselective conversion of D-glucuronolactone into pseudosugar: Synthesis of pseudo-α-D-glucopyranose, pseudo-β-D-glucopyranose, and validamine

Article abstract of DOI:10.1016/S0040-4020(01)85530-7

Two optically active pseudo-sugars, pseudo-α-D-glucopyranose (12) and pseudo-β-D-glucopyranose (13), were synthesized from D-glucuronolactone in favorable overall yields by using a stereoselective nitromethane addition reaction and a reductive elimination of an ethoxyethoxyl moiety with NaBH₄ as key steps. Furthermore, a biologically active pseudo-aminosguar, validamine (18) was efficiently synthesized via a substitution reaction for an acetoxyl group at the β-position of nitro group in a nitrocyclitol derivative (14) which was prepared from a synthetic intermediate (9) of pseudo-d-glucopyranoses (12,13).