FACILE SYNTHESIS OF 3'-O-METHYLTHYMIDINE AND 3'-DEOXYTHYMIDINE AND RELATED DEOXYGENATED THYMIDINE DERIVATIVE - A NEW METHOD FOR SELECTIVE DEOXYGENATION OF SECONDARY HYDROXY-GROUPS

This paper deals with convenient syntheses of 3'O-methylthymidine (2) and 3'-deoxythymidine (3), which involve Ag2O-promoted methylation and Barton-Robins reductive deoxygenation, respectively. New methods for the regioselective 3'- and 5'-deoxygenation of thymidine have also been developed. Namely, compound 3 was synthesized by the 3‘-5'-O-diacylation of thymidine with phenyl chlorothionoformate (PTCF) followed by the selective 3'-reduction with tributyltin hydride and successive alkaline hydrolysis. 5'-Deoxythymidine (18) was obtained by the 5'-selective acylation of thymidine with PTCF followed by reduction with tributyltin hydride. © 1990, American Chemical Society. All rights reserved.