A general scheme for the synthesis of ribonucleotides containing an alkoxymethyl group at the 2′-O-position of ribose and an O-nucleophilic catalytic 4-methoxy-1-oxido-2-picolyl phosphate-protecting group has been developed for the introduction into oligonucleotides during their solid-phase synthesis by the phosphotriester method. The scheme has been tested in the synthesis of monomers with 2′-O-modifying groups as examples: 2-azidoethoxymethyl, propargyloxymethyl, and 3,4-cyclocarbonatebutoxymethyl groups. © 2011 Pleiades Publishing, Ltd.