Phosphorylation of 1-(2-deoxy-β-D-xylofuranosyl)thymine(1)or 9-(2-deoxy-β-D-xylofuranosyl)adenine(3)with phosphoryl chloride gives the cyclic 3′,5′-phosphates(2and4a) but not the 5′-monophosphates8aor8b. The latter are obtained by phosphorylation of the 3′-0-benzoylated 2′-deoxy-β-D-xylonucleosides(7a, b)and subsequent base-catalyzed removal of the benzoyl groups. Compound 3, as the parent dA, depurinates in acidic medium, a reaction which is facilitated in the case of the N6-benzoyl derivative9band reduced after the introduction of an amidine protecting group. N-Glycosylic bond hydrolysis of 2′-deoxy-β-D-xylofuranosyl nucleosides is enhanced by a factor of two compared to 2′-deoxy-β-D-ribofuranosyl nucleosides.