Lipozyme® TL IM mediated the selective deacetylation of one of the two acetoxy groups in 4-C-acetoxymethyl-5-O-acetyl-3-azido-3-deoxy-1,2-O-isopropylidene-α-d-xylofuranose, leading to the first efficient syntheses of 3′-azido/3′-amino-xylobicyclonucleosides T, U, C and A.