α-D-ALLOPYRANOSYL β-D-FRUCTOFURANOSIDE (allo-SUCROSE) AND ITS DERIVATIVES

Article abstract of DOI:10.1016/S0008-6215(00)85433-6

Reduction of 3-ketosucrose (1) with sodium borohydride gave mainly α-D-allopyranosyl β-D-fructofuranoside (2), characterised as its octabenzoate.Using sodium borodeuteride, <3-(2)H>allo-sucrose (5) and <3-(2)H>sucrose (6) were obtained in the ratio 12:1.The mixture was fractionated on Dowex-50 X8 resin , and the <3-(2)H> derivatives were isolated as their octa-acetates.Inspection of the (13)C-n.m.r. spectra of 5 and 6 enabled the C-3 signals to be assigned, allo-Sucrose (2) was more readily obtained by oxidation of sucrose with dimethyl sulphoxide-acetic anhydride followed by reduction with sodium borohydride and fractionation on Dowex-50 X8 resin.Tritylation of 2 followed by acetylation gave, after chromatography, the 6,1',6'-tritrityl ether (9, 10percent), the 6,6'-ditrityl ether (10, 26percent), and a mixture of monotrityl ethers (20percent).Hydrogenolysis of 9 and 10 gave the penta-acetate and hexa-acetate, respectively, with no detectable migration of AcO-4.Treatment of 2 with sulphuryl chloride at -50 degC gave the 6,6'-dichloride.