New synthesis of 1-deoxyhexuloses

Abstract

By displacement of a nitrobenzene-p-sulphonyloxy group by iodide ion from position 1 of 2,3:4,6-di-O-isopropylidene-α-L-sorbofuranose and 2,3:4,5-di-O-iso-propylidene-β-D-fructopyranose, and subsequent hydrogenolysis, 1-deoxy-L-sorbose and 1-deoxy-D-fructose, respectively, have been synthesized. Inversion by oxidation with ruthenium tetroxide, and subsequent reduction, provided new syntheses of D-tagatose and 1-deoxy-L-psicose. The N.M.R. spectrum shows that the aqueous solution of 1-deoxy-D-fructose contains a considerable proportion of the keto form; this proportion increases with increasing temperature.