Synthesis of the New Types of <i>N</i>‐Unsubstituted Aminomethylenebisorganophosphorus Acids and Their Derivatives

Prishchenko, A. A.; Ливанцов, М. В.; Livantsova, L. I.; Ershov, I. S.; Petrosyan, V. S.

doi:10.1002/hc.21220

Cited by 11 publications

(3 citation statements)

References 14 publications

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“…The access to AMBPs is documented in the literature [26]. Indeed, several approaches present the do phosphonylation of amides and nitriles mediated by various Lewis acids [27][28][29][30], a t component reaction of amines with orthoformate and phosphites [31][32][33][34][35][36][37][38][39][40], an Beckmann transposition of oximes in the presence of phosphites [41,42] (Figure Alternatively, only limited examples were reported for the synthesis aminomethylenebisphosphinates (AMBPi) and their biological activities remain unkn to date [43][44][45]. Here, the strategy usually consists of adding in situ pre-formed BTSP ethyl formimidate hydrochloride or onto substituted amides in the presence of TMS respectively (Figure 2c).…”

Section: Introductionmentioning

confidence: 99%

Synthesis of Aminobisphosphinates through a Cascade Reaction between Hypophosphorous Acid and Bis(trimethylsilyl)imidates Mediated by ZnI2

Ayadi,

Descamps,

Legigan

et al. 2023

Molecules

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Among phosphorylated derivatives, phosphinates occupy a prominent place due to their ability to be bioisosteres of phosphates and carboxylates. These properties imply the necessity to develop efficient methodologies leading to phosphinate scaffolds. In recent years, our team has explored the nucleophilic potential of silylated phosphonite towards various electrophiles. In this paper, we propose to extend our study to other electrophiles. We describe here the implementation of a cascade reaction between (trimethylsilyl)imidates and hypophosphorous acid mediated by a Lewis acid allowing the synthesis of aminomethylenebisphosphinate derivatives. The present study focuses on methodological development including a careful NMR monitoring of the cascade reaction. The optimized conditions were successfully applied to various aliphatic and aromatic substituted (trimethylsilyl)imidates, leading to the corresponding AMBPi in moderate to good yields.

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Section: Introductionmentioning

confidence: 99%

Synthesis of Aminobisphosphinates through a Cascade Reaction between Hypophosphorous Acid and Bis(trimethylsilyl)imidates Mediated by ZnI2

Ayadi,

Descamps,

Legigan

et al. 2023

Molecules

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“…Recently some of the N-substituted aminomethylenediphosphonates have been synthesized by us using various formamides and their derivatives like dialkylformamide dialkylacetals and ethoxymethylene imines as well as trimethylsilyl esters of trivalent organophosphorus acids with PH and POSiMe 3 moieties. [4][5][6][7] …”

Section: Introductionmentioning

confidence: 99%

“…Also these diphosphonates with hard hydrolysable P–C–P structure such as zoledronic, risedronic, and minodronic acids are widely used in medicine as well known drugs—regulators of calcium metabolism. Recently some of the N ‐substituted aminomethylenediphosphonates have been synthesized by us using various formamides and their derivatives like dialkylformamide dialkylacetals and ethoxymethylene imines as well as trimethylsilyl esters of trivalent organophosphorus acids with PH and POSiMe 3 moieties …”

Section: Introductionmentioning

confidence: 99%

Synthesis of new functionalized mono‐ and diphosphonic acids with five‐membered aza‐heterocycles moieties

Prishchenko

Alekseyev

Ливанцов

et al. 2016

Heteroatom Chemistry

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The new functionalized hydroxymethylphosphonic and methylenediphosphonic acids are synthesized via unique reaction of tris(trimethylsilyl)phosphite and Nformyl derivatives of five-membered aza-heterocycles at the presence of effective catalyst-trimethylsilyl triflate. Trimethylsilyl esters 1,2 readily react with excess methanol under mild conditions to form water-soluble functionalized mono-or diphosphonic acids, respectively, 3,4 (Scheme 3).The resulting compounds 1-4 can be used for the synthesis of new types of organophosphorus substances, including both heterocyclic fragments and phosphonic groups. These compounds are promising precursors for multitarget drug discovery, perspective plant growth regulators, as well as effective polydentate ligands for various metal complexes with versatile properties.It should be noted that, unlike diethyl acetal formamides, which react readily with esters of phosphorous acid to form N-substituted aminomethylenediphosphonates, [10] reaction of readily available N-diethoxymethyl derivatives of azaheterocycles [11][12][13] with tris(trimethylsilyl) phosphite proceeds via rupture of C-N bonds and leads to diethoxymethylphosphonates 5 in high yields (Scheme 4). | CONCLUSIONSThus, we have proposed the convenient methods of synthesis of new functionalized mono-and diphosphonic acids with five-membered aza-heterocycles moieties via the unique reaction of tris(trimethylsilyl) phosphite with N-formyl azaheterocycles catalyzed by trimethylsilyl triflate. | EXPERIMENTAL | Bis(trimethylsilyl) 1H-imidazol- 1-yl(trimethylsiloxy)methylphosphonate (1a) and tetra(trimethylsilyl) 1H-imidazol-1-ylmethylenediphoshonate (2a)A solution of symm-dicyclohexylcarbodiimide (14.4 g, 0.07 mol) in CH 2 Cl 2 (20 mL) was added under stirring to a solution of 1H-imidazole (3.4 g, 0.05 mol) and formic acid (2.8 g, 0.06 mol) in CH 2 Cl 2 (50 mL). The mixture was stirred for 6 hours and left for 12 hours, then the precipitate is filtered off, the resulting solution was added to a solution of tris(trimethylsilyl) phosphite (44.8 g, 0.15 mol), and a solution of trimethylsilyl triflate (2.9 g, 0.013 mol) in CH 2 Cl 2 (10 mL) was added to this mixture. The mixture was heated in a boiling water bath to complete the stripping of low-boiling compounds and then distilled to give 1.8 g of phosphonate 1a, yield 9%, bp 102°C (1 mm Hg) and diphosphonate (22.0 g) 2a, yield 83%, bp 126°C (1 mm Hg). 4. | 1H-Imidazol-1-yl(hydroxy) methylphosphonic acid (3a)Yield 96%, mp 144-145°C (decomposition ).Phosphonate 5b was obtained similarly.

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Synthesis of Substituted N‐Formylaminomethylenediphosphonates and Their Derivatives

Prishchenko

Ливанцов

Livantsova

et al. 2015

Heteroatom Chemistry

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The convenient methods for the synthesis of new trimethylsilyl esters of aminomethylenediphosphonic acids are elaborated. The new substituted N‐formylaminomethylenediphosphonates are obtained via the interaction of trimethylsilyl esters of methylenediphosphonic acids with a mixture of triethyl orthoformate and ethanol. Also boron trifluoride–diethyl etherate as an effective catalyst is used for the interaction of hydrochlorides of ethoxymethylene imines with diethyl trimethylsilyl phosphite. The corresponding aminomethylenediphosphonic acids are presented.

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Synthesis of the New Types of N‐Unsubstituted Aminomethylenebisorganophosphorus Acids and Their Derivatives

Cited by 11 publications

References 14 publications

Synthesis of Aminobisphosphinates through a Cascade Reaction between Hypophosphorous Acid and Bis(trimethylsilyl)imidates Mediated by ZnI2

Synthesis of Aminobisphosphinates through a Cascade Reaction between Hypophosphorous Acid and Bis(trimethylsilyl)imidates Mediated by ZnI2

Synthesis of new functionalized mono‐ and diphosphonic acids with five‐membered aza‐heterocycles moieties

Synthesis of Substituted N‐Formylaminomethylenediphosphonates and Their Derivatives

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