Coupling reaction between 2-α-phenylthio-2, 3-dideoxyribose and silylated pyrimidine bases in the presence of SnCl 4 proceeded stereoselectively to give the β-anomers. These nucleosides were converted to 2′, 3′-dideoxy-2′, 3′-didehydronucleosides by oxidation followed by thermal elimination.