SYNTHESIS OF 5'-FLUORO-5'-DEOXYTOYOCAMYCIN AND 5'-AMINO-5'-DEOXYTOYOCAMYCIN AND SANGIVAMYCIN AND SOME RELATED DERIVATIVES

A series of 5'-substituted analogs of toyocamycin were prepared by con densation of silylated 4-amino-6-bromo-5-cyanopyrrolo[2,3-d]pyrimidine with protected 5-azidod-deoxy- or 5-fluoro-5-deoxyribofuranose follow ed by debromination and deblocking. Alternatively, 5'-azido-5'-deoxyto yocamycin was prepared by azidation of toyocamycin. Conversion of the 5-nitrile function of the toyocamycin derivatives into a carboxamide o r a thiocarboxamide gave the corresponding analogs of sangivamycin or thiosangivamycin while reduction of the 5'-azido-5'-deoxy nucleosides provided 5'-amino-5'-deoxy derivatives.