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Organosilicon-mediated synthesis of functionalized organophosphorus acids and their derivatives was used recently by us as convenient method of creating of P-C bonds. We have synthesized the new functionalized methylenediphosphonic acids and their derivatives 1 including aromatic, azaheterocyclic, and amino acids moieties via addition of tris(trimethylsilyl) phosphite to corresponding formamides in the presence of effective catalyst – trimethylsilyl triflate under mild conditions. Also trimethylsilyl-containing organophosphorus compounds easily react with methanol excess or with sodium methylate in methanol giving water soluble acids or their sodium salts in high yields.