SYNTHESIS OF PORPHYRINYL-NUCLEOSIDES

Several porphyrinyl-nucleosides were prepared in the reaction of the OH group of one, two or four meso-p-hydroxyphenyl substituents of porphyrin with 5'-O-tosylates of 2',3'-O-isopropylidene-adenosine or -uridine, or 5'-O-tosylthymidine; the remaining porphyrin meso-substituents were p-tolyl, p-hydroxyphenyl or 4-pyridyl. The following porphyrinyl-nucleosides were obtained with 8-17% yield: meso-di(p-tolyl)di(p-phenylene-5'-O-2',3'-O-isopropylidene-adenosine) (or -uridine)porphyrins 1,2, the respective meso-tetranucleosideporphyrins 3,4-meso-mono(p-phenylene-5'-O-thymidine)porphyrins 5-7, meso-di(p-tolyl)di(p-phenylene-5'-O-thymidine) porphyrins 8,9 and the meso-di(p-hydroxyphenyl)di(p-phenylene-5'-O-thymidine)porphyrins 10. Other compounds prepared belonged to the series: meso(4-pyridyl)4-n(p-phenylene-5'-O-2',3'-O-isopropyli-deneuridine)(n)porphyrin, n = 1, 2 or 4, 11-13. N-Methylation gave the water soluble iodide salts: (N-methyl-4-pyridinium)4-n(p-phenylene-5'-O-2',3'-isopropylideneuridine)(n)porphyrins, n = 1, 2 or 4, 14-16. The ms fab showed in most cases stepwise detachment of the CH2(5')-nucleoside fragments. The porphyrins meso disubstituted by thymidine represent a convenient substrate for the build-up of both nucleoside units into the oligo/polynucleotide chains.