Diacetone-D-glucosyl-3-O-(N,N-diethylamido)-thiophosphates of the lipid-soluble vitamins D₂, D₃ and E

Abstract

The acyclic triamides of phosphorous acid, after appropriate activation, offer a number of advantages over conventional reagents when biologically active lipids are to be phosphorylated. The hexaethyltriamide of phosphorous acid activated by addition of iodine at the optimum molar ratio of 1.05∶0.05 was used as phosphorylating reagent to synthesize diacetone-D-glucosyl-3-0-(N,N-diethylamido)thiophosphates of ergocalciferol, cholecalciferol and DL-α-tocopherol in a “one-pot” procedure in overall yields of 83–87%. The high selectivity of the phosphorylation at the monoester formation stage permits the direct synthesis of asymmetrical diesters. Anisochronicity was detected in the¹³C and³¹P nuclear magnetic resonance spectra of the thiophosphates synthesized. The compounds represent new types of glycophospholipid structures which, in addition to carbohydrate and a phosphagen fragment, contain a lipid-soluble vitamin.