SYNTHESES OF THYMIDINE DIPHOSPHOGLUCOSE DERIVATIVES

Per-O-benzoylated 3- and 4-deoxy-alpha-D-glucopyranoses 3 and 12, as w ell as the respective 4-isobutyramido derivative 29 were converted int o their hemiacetals, phosphitylated, and oxidized to yield anomeric mi xtures of glycosyl phosphates. These partially esterified compounds we re coupled with dTMP morpholidate to give after complete deblocking dT DP-3-deoxy-alpha-D-glucose (11), dTDP-4-deoxy-alpha-D-glucose (19) and dTDP-4-amino-4-deoxy-alpha-D-glucose (36). 3-Acetamido-3-deoxy-alpha- D-glucopyranosyl phosphate was synthesized according to the silver dip henyl phosphate procedure and subsequently converted into dTDP-3-aceta mido-3-deoxy-alpha-D-glucose (dTDP-N-acetyl-D-kanosamine) (26) by hydr ogenation and coupling with dTMP morpholidate.