Nucleosides. CIX. 2′-Deoxy-ψ-isocytidine, 2 -deoxy-ψ-uridine,and 2′-deoxy-l-methyl-ψ-uridine. Isosteres of deoxycytidine,deoxyuridine and thymidine

2′-Deoxy-ψ-isocytidine (VIIβ), a 2′-deoxy analog of antileukemic ψ-isocytidine and also a C-nucleoside analog of deoxycytidine, was synthesized from ψ-uridine by making use of the newly discovered pyrimidine to pyrimidine transformation reaction J. Chem. Soc., 14, 537 (1977)]. 2′-Deoxy-ψ-uridine (IIβ) and 2′-deoxy-l-methyl-ψ-uridine (V), both C-nucleoside analogs of deoxyuridine and thymidine, were also synthesized. ψ-Uridine was converted into the 2′-chloro analogs (I) which was reduced with tributyltin hydride to give an α,β-mixture of 2′-deoxy-ψ-uridines. The β-isomer (11β was trimethylsilylated and the product (III) treated with methyl iodide to afford the 1-methyl derivative (IV). After hydrolytic removal of the trimethylsilyl groups from IV, the thymidine analog (V) was obtained in good yield. A crude mixture of II was converted in good yield into an α,β-mixture of 1,3-dimethyl-2 -deoxy-ψ-uridines (VI) by treatment with DMF dimethyl acetal in DMF. Treatment of the β-isomer (VIβ) with guanidine, however, gave the α,β-mixture of 2 -deoxy-ψ-isocytidines (VII). The pure β-isomer (VIIβ) was obtained by thick layer chromatography. The pure α-isomer (VIIα) was obtained when VIα was treated with guanidine. 2 -Deoxy-ψ-isocytidine (VIIβ) and 2 -deoxy-l-methyl-ψ-uridine (V) exhibited inhibitory activity against P815 cells (ID_{5 0} 1.2 μg./ml. and 4.9 μg./ml., respectively) and the thymidine analog V was found to be active against Streptococcus faecium var. duran. J. Heterocyclic Chem., 14, 1119 (1977)