The new mono- and bis(aminomethylenediphosphonic) acids are synthesized for the first time via unique reaction of tris(trimethylsilyl) phosphite and various N-formyl amino alkanols or bis(N-formyl amino) alkanes at the presence of effective catalyst - trimethylsilyl triflate under mild conditions. The further treatment of initially formed trimethylsilyl intermediates with the methanol excess resulted in the crystalline mono- and bis(aminomethylenediphosphonic) acids in high yields. The catalytic scheme of target substances formation is proposed and discussed in detail. The structures of target acids were confirmed by the H-1, C-13, P-31 NMR spectra and high resolution mass spectra (HRMS). The resulting compounds are of great interest as perspective bioactive substances with versatile properties and effective polydentate ligands. (C) 2021 Elsevier B.V. All rights reserved.

The new non-proteinogenic amino acids with methylenebisphosphonic acids moieties are synthesized for the first time via unique reaction of tris(trimethylsilyl) phosphite and various N-formyl amino acids at the presence of effective catalyst - trimethylsilyl triflate under mild conditions . The further treatment of initially formed trimethylsilyl intermediates with the methanol excess resulted in the water-soluble non-proteinogenic amino acids with methylenebisphosphonic acids moieties in high yields. The catalytic scheme of target substances formation is proposed and discussed in detail. The structures of target functionalized amino acids and their precursors were confirmed by the H-1, C-13, P-31 NMR spectra and high resolution mass spectra. The resulted compounds are of great interest as promising antiviral substances and effective ligands. (C) 2021 Elsevier B.V. All rights reserved.

The new convenient synthesis of functionalized aryl and pyridyl aminomethylenebisphosphonic acids and their derivatives has been developed via silicon-assisted methodology. New functionalized amino-methylenebisphosphonic acids containing pyridines moieties were obtained using unique reaction of tris(trimethylsilyl) phosphite with N-formyl aminopyridines and trimethylsilyl triflate as a catalyst under mild conditions. Intermediates - tetra(trimethylsilyl) aminomethylenebisphosphonates formed, were converted to the target acids by further treatment with methanol excess. In contrast the corresponding tetraethyl aminomethylenebisphosphonates were synthesized under heating (130 degrees C) of four component mixture (diethyl trimethylsilyl phosphite, triethyl orthoformate, aryl- or pyridylamine, and diethyl phosphite) in the presence of zinc chloride catalyst. The catalytic schemes of target substances formation are proposed and thoroughly discussed. (C) 2020 Elsevier B.V. All rights reserved.

The convenient silicon-assisted synthesis of new aminomethylenebisphosphonic acids and their precursors was developed via unique methodology. So new aminomethylenebisphosphonic acids with quinolines moieties were obtained using suitable reaction of tris(trimethylsilyl) phosphite and N-formyl aminoquinolines catalyzed by trimethylsilyl triflate under mild conditions (20 degrees C). The initially formed intermediates - tetra (trimethylsilyl) aminomethylenebisphosphonates are transformed to target acids by methanolysis in high yields. The catalytic scheme of target substances formation is proposed and discussed in detail. The structures of aminomethylenebisphosphonic acids and their precursors with substituted quinoline moieties were confirmed by the H-1, C-13, P-31 NMR spectra and high resolution mass spectra. (C) 2020 Elsevier B.V. All rights reserved.

The convenient synthesis of new functionalized organophosphorus acids and their derivatives containing indan moieties was developed. The regioselective radical addition of bis(trimethylsiloxy)phosphine to indene proceeds to give rise to 2-indanylphosphonite as key compound for preparation of above acids with bicyclic substituents. Azobis(isobutyronitrile) (AIBN) in the conditions of its thermolysis was used as effective initiator of the addition reaction. The further treatment of organophosphorus acids trimethylsilyl esters with the methanolic sodium methoxide solution resulted in the water-soluble sodium salts of the corresponding acids.

The new functionalized aminomethylenediphosphonates with moieties of various amino acids are synthesized via unique reaction of tris(trimethylsilyl) phosphite and N-formyl amino acids at the presence of effective catalyst – trimethylsilyl triflate under mild conditions. The further treatment of aminomethylenediphosphonates with the methanol excess resulted in the water-soluble functionalized aminomethylenediphosphonic acids.

The convenient synthesis of new aminomethylphosphinic acids and their derivatives containing N-alkyl 4-hydroxypiperidines moieties was developed. The addition of bis(trimethylsiloxy)phosphine to N-alkyl 4-piper-idones proceeds under mild conditions to give PH-phosphinates as key compounds for preparation of trimethylsilyl esters of above acids via interaction with various aminals. The further treatment of phosphinic acids trimethylsilyl esters with the methanol resulted in the water-soluble corresponding acids. The structures of aminomethylphosphinic acids and their precusors 1-3 with substituted piperidine moieties were confirmed by the H-1, C-13, P-31 NMR spectra.

The new functionalized hydroxymethylphosphonic and methylenediphosphonic acids are synthesized via unique reaction of tris(trimethylsilyl) phosphite and N-formyl N-heterocycles, N-substituted 4-piperidones, 3-quinuclidone, and 2-adamantanone at the presence of effective catalyst – trimethylsilyl triflate under mild conditions.

The various methods of aminomethylation of some PH-acids with proline and their derivatives are investigated. The numerous derivatives of proline and corresponding phosphonates, phosphonites, phosphinates, and phosphorane with proline moieties are presented.

The convenient methods of syntheses of new organophosphorus methane- and 4-substituted benzenenesulfonylamides from the trivalent organophosphorus acid esters and reactive N-chloromethyl N-methyl methanesulfonylamide, phosphorylated methylamines with NH-and NSi moieties and methane- and 4-substituted benzenesulfonyl chlorides were developed. The new types of functionalized organophosphorus derivatives of methane- and 4-substituted benzenesulfonic acids with P-C-N moieties were afforded in good yields.

The new functionalized hydroxymethylphosphonic and methylenebis(phosphonic) acids are synthesized via reaction of tris(trimethylsilyl) phosphite and N-formyl derivatives of five-membered N-heterocycles in the presence of trimethylsilyl triflate.

The addition of trimethylsilyl esters of trivalent phosphorus acids to trimethylsilyl ester of 1 H-indene-3-carboxylic acid has been studied. The convenient syntheses of new functionalized organophosphorus acids and their derivatives with indan-1-carboxylic acid moieties have been proposed. Water-soluble sodium salts of the corresponding acids were also obtained.

The convenient syntheses of new organophosphorus-substituted benzofulvenes with indenyl moieties from bis(trimethylsilyl) inden-2-ylphosphonate and substituted azomethines in the presence of the effective initiator-sodium hydride are developed. The following treatment of phosphonates with methanolic sodium methylate gives stable water-soluble disodium salts of corresponding phosphonic acids.

\ The new functionalized hydroxymethylphosphonic and methylenediphosphonic acids are synthesized via unique reaction of tris(trimethylsilyl) phosphite and N-formyl derivatives of five-membered aza-heterocycles at the presence of effective catalyst-trimethylsilyl triflate.