Studies on nucleosides and nucleotides. VIII. Preparation and reactions of triphenylphosphoranediylnucleosides.

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The reaction of uridine, N4-benzoylcytidine, guanosine, and N6-p-toluoyladenosine with diethyl azodicarboxylate and triphenylphosphine resulted in the formation of the corresponding 2′,3′-O-(triphenylphosphoranediyl)-cyclonucleosides. On the other hand, adenosine afforded, under similar conditions, 3′,5′-O-(triphenylphosphoranediyl)adenosine (19). The difference can be explained in terms of the acidity of base moieties of the nucleosides. The reaction of 2′,3′-O-(triphenylphosphoranediyl)-O2,5′-cyclouridine, N4-benzoyl-2′,3′-O-(triphenylphosphoranediyl)-O2,5′-cyclocytidine, 2′,3′-O-(triphenylphosphoranediyl)-N3,5′-cycloguanosine, or N6-p-toluoyl-2′,3′-O-(triphenylphosphoranediyl)-N3,5′-cycloadenosine with nucleophiles and with electrophiles addorded the corresponding nucleoside derivatives with free 2′- and 3′-hydroxyl groups. Thus the 2′,3′-O-triphenylphosphoranediyl group serves as a protecting group which is readily removed during work-up of the reaction products. 19 reacted with phenyl isocyanate to give 5′-O-phenylcarbamoyladenosine and N6,5′-O-bis(phenylcarbamoyl)adenosine. The reaction of 19 with diphenylketene also afforded acyladenosines with free 2′- and 3′-hydroxyl groups. These results suggested that 3′,5′-O-triphenyl phosphoranediyl group activates the 5′-carbon atom of adenosine.
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