Chemical and Enzymatic Syntheses of 6-Deoxyhexoses. Conversion to 2,5-Dimethyl-4-hydroxy-2,3-dihydrofuran-3-one (Furaneol) and Analogues

Abstract

6-Deoxy-D-fructose 1-phosphate (6-deoxyF-l-P) forms when a solution containing D-fructose 1,6-diphosphate (FDP) and D-lactaldehyde is treated with the enzymes aldolase and triosephosphate isomerase (Scheme I). This transformation involves three reactions: aldolase-catalyzed cleavage of FDP to a mixture of dihydroxyacetone phosphate and D-glyceraldehyde phosphate, triosephosphate isomerase catalyzed equilibration of dihydroxyacetone phosphate and D-glyceraldehyde phosphate, and aldolase-catalyzed condensation of dihydroxyacetone phosphate and D-lactaldehyde to 6-deoxyF-l-P. An analogous process converts a mixture of FDP and L-lactaldehyde to 6-deoxysorbose 1-phosphate (6-deoxyS-l-P). Aldolase-catalyzed reaction of dihydroxyacetone phosphate, prepared separately, with D-lactaldehyde yields 6-deoxyF-l-P directly; similar reaction of dihydroxyacetone phosphate with -hydroxybutyraldehyde yields a mixture of 6-methyl-6-deoxyhexose 1-phosphates. Acid-catalyzed hydrolysis of the sugar phosphates releases the corresponding free sugars. A mixture containing 6-deoxyhexoses is formed directly by base-catalyzed aldol condensation of dihydroxyacetone and D,L-lactaldehyde. Treatment of any of the 6-deoxyhexoses with acids generates 2,5-dimethyl-4-hydroxy-2,3-dihydrofuran-3-one (Furaneol, a flavor principle). Furaneol can also be prepared in moderate yields by hydrogenolysis of FDP and other hexose phosphates in alkaline media. © 1983, American Chemical Society. All rights reserved.