The direct preparation of mannosyl[2]rotaxane derivatives by O-glycosylation from tetra-O-acetyl-rs/alpha.gif" BORDER=0>-D-mannosyltrichloroacetimidate and a tert-butylanilinium alcohol in the presence of dibenzo-24-crown-8 is described. The method appears to be very efficient and allows for the preparationof either orthoester or mannosyl rotaxane derivatives, depending on reaction conditions.