DERIVATIZATION OF 1,3,4,6-TETRA-O-BENZOYL-ALPHA-D-FRUCTOFURANOSE AT THE ANOMERIC SITE - O-ALKYLATION, O-ACYLATION, O-ARYLATION, AMINATION AND SELENATION REACTIONS

Treatment of D-fructose with benzoyl chloride gave either 1,2,3,4,6-penta-O-benzoyl-alpha-D-fructofuranose or 1,3,4,6-tetra-O-benzoyl-alpha-D-fructofuranose (1-alpha) which with methanol, 2-nitrophenol, or 4-nitrophenol in the presence of the Mitsunobu reagents, diisopropyl azodicarboxylate and triphenylphosphine, gave the corresponding fructofuranosides in good yield; an analogous reaction with 4-methoxybenzylamine gave the corresponding D-fructo-furanosylamine. Alkylation with isopropyl alcohol or t-butyl alcohol was complicated by competition from transesterification and fructose disaccharide formation. There was little or no inversion in these reactions. The 2-O-acetyl derivative of 1 reacted with selenophenol and diethyl ether-boron trifluoride to give phenyl 1-deoxy-3,4,6-tri-O-benzoyl-2-seleno-alpha,beta-D-fructofuranose as a minor product and phenyl 1,3,4,6-tetra-O-benzoyl-2-seleno-alpha,beta-D-fructofuranose which with tris(trimethylsilyl)silane and AIBN gave 1,3,4,6-tetra-O-benzoyl-2,5-anhydro-D-mannitol and 1,3,4,6-tetra-O-benzoyl-2,5-anhydro-D-glucitol. Treatment of the acetyl derivative of 1 with Me3SiN3 gave 1,3,4,6-tetra-O-benzoyl-alpha,beta-D-fructofuranosyl azide which was hydrogenated to afford the corresponding fructofuranosylamine. This compound rearranged to give N-benzoyl-1,4,6-tri-O-benzoyl-beta-D-fructofuranosylamine.