Diastereomerically Pure Nucleoside-5′-O-(2-thio-4,4-pentamethylene-1,3,2-oxathiaphospholane)s-Substrates for Synthesis of P-Chiral Derivatives of Nucleoside-5′-O-phosphorothioates

A method for stereocontrolled chemical synthesis of P-substituted nucleoside 5'-O-phosphorothioates has been elaborated. Selected 3'-O-acylated deoxyribonucleoside-and 2',3'-O,O-diacylated ribonucleoside-5'-O-(2-thio-4,4-pentamethylene-1,3,2-oxathiaphospholane)s were chromatographically separated into P-diastereomers. Their reaction with anions of phosphorus-containing acids was highly stereoselective (>= 90%) and furnished corresponding P-chiral alpha-thiodiphosphates and their phosphonate analogs with satisfactory yield. Chirality 23: 237-244, 2011. (C) 2010 Wiley-Liss, Inc.