STUDIES ON PHOSPHORYLATION .4. SELECTIVE PHOSPHORYLATION OF PRIMARY HYDROXYL GROUP IN NUCLEOSIDES

Nucleoside 5ʹ-phosphates of a number of naturally occurring and synthetic purine and pyrimidine ribonucleosides and their 2ʹ-deoxy and 2ʹ-O-methyl derivatives were prepared in good yields by direct phosphorylation of their corresponding unblocked nucleosides with pyrophosphoryl chloride in m-oresol or o-chlorophenol. Similar treatment of purine and pyrimidine arabino- and gluconucleosides, and aristeromycin resulted in the selective phosphorylation of the primary hydroxyl groups to give the corresponding phosphates. α-Guanosine and 2ʹ-deoxyadenosine gave the 5ʹ-phosphates in relatively low yield. The 5ʹ-phosphate and 3ʹ,5ʹ-cyclic phosphate were obtained from 9-β-D-xylofuranosyladenine. Acetonitrile, benzonitrile, ethyl acetate, methyl acrylate, ethyl benzoate and nitrobenzene, when used as solvents, gave satisfactory results in the direct phosphorylation reaction. © 1969, American Chemical Society. All rights reserved.