Phosphoenolpyruvate as a dual purpose reagent for integrated nucleotide/nicotinamide cofactor recycling.

An efficient technique is presented which integrates cofactor dependent enzymic phosphorylation and dehydrogenation into a single, closed-loop system by employing phosphoenolpyruvate as the sacrificial reagent for sequential ATP and NAD+ recycling steps. Exemplary applications are developed for the synthesis of 6-phosphogluconate from glucose, and that of dihydroxyacetone phosphate from glycerol. The latter system is combined with exergonic diastereoselective aldol additions for the one-flask synthesis of a ketosugar (D-sorbose), thiosugar (L-threo-5-thiopentulose), or a sugar acid (L-threo-pent-4-ulosonic acid) starting from a mixture of glycerol and simple aldehydes.