An improved synthesis of dihydroxyacetone phosphate

Article abstract of DOI:10.1016/S0040-4020(01)81796-8

An improved procedure has been developed for the synthesis of dihydroxyacetone phosphate (DHAP). Reaction of 2,5-diethoxy-p-dioxane-2,5-dimethanol (1) and the trivalent phosphorylating reagent dibenzyl-N,N-diethylphosphoramidite (DDP) in the presence of 1,2,4-triazole or tetrazole followed by oxidation with H₂O₂ gave 2,5-diethoxy-p-dioxane-2,5-dimethanol-O-2¹-O-5¹-bis(phosphate) tetrabenzyl ester (2) in 98% yield. Compound 2 was then hydrogenated in the presence of H₂-Pd/C to give, after neutralization, 2,5-diethoxy-p-dioxane-2,5-dimethanol-O-2¹-O-5¹-bis(phosphate) as a stable trisodium salt (3) in 84% yield. Treatment of 3 with Dowex 50 (H⁺) generates 2 equivalents of DHAP.