Synthesis of porphyrinyl‐nucleosides

Abstract

AbstractSeveral 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‐isopropylideneuridine)nporphyrin, n = 1, 2 or 4, 11–13. N‐Methylation gave the water soluble iodide salts: (N‐methyl‐4‐pyridinium)44−n(p‐phenylene‐5′‐O‐2′,3′‐isopropylideneuridine)nporphyrins, 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.