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Functionalized methylenediphosphonic acids and their derivatives with aromatic and heterocyclic moieties are well-known biomimetics of hydroxy- or aminocarboxylic acids and natural pyrophosphates, and some of them such as zoledronic, risedronic, and minodronic acids are widely used in medicine. 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.