Phosphoric, Phosphonic, and Phosphinic Acid Amides as Bases

Matrosov, E. I.; Kryuchkov, A. A.; Nifantyev, E. E.; Kozachenko, A. G.; Кабачник, М. И.

doi:10.1080/03086648208078983

Cited by 7 publications

(6 citation statements)

References 1 publication

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“…Consequently, the modification P-NH 2 is not protonated between pH 5.45 and 7. This result is in accord with the known low basicity of phosphoric amide diesters (18,33,34). In contrast, the stability of the 'parent' duplex d(Tp) 11 dT-9 increases with increasing NaCl concentration as expected.…”

Section: Base-pairing Of Oligonucleotide Analogues With Dna and Rna C...supporting

confidence: 88%

“…It is assumed that the influence of a modification on the stabilities of duplexes also results from the disturbance of the spin of hydration around the modified phosphate groups (8,17). The amides of phosphorus acid are known to have good solvating properties (18). Furthermore, in phosphoramidates (P-NH 2 ), the fact that the NH 2 group is small, uncharged in aqueous solution and forms hydrogen bonds readily (19), gives them favourable solubility characteristics required for hydration, with a minimum steric hindrance around the phosphorus atom, and makes them attractive potential candidates for non-anionic analogues of oligonucleotides.…”

Section: Introductionmentioning

confidence: 99%

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Oligodeoxynucleoside phosphoramidates (P-NH2): synthesis and thermal stability of duplexes with DNA and RNA targets

Peyrottes

1996

Nucleic Acids Research

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Syntheses of non ionic oligodeoxynucleoside phosphoramidates (P-NH2) and mixed phosphoramidate- phosphodiester oligomers were accomplished on automated solid supported DNA synthesizer using both H-phosphonate and phosphoramidite chemistries, in combination with t-butylphenoxyacetyl for N-protection of nucleoside bases, an oxalyl anchored solid support and a final treatment with methanolic ammonia. Thermal stabilities of the hybrids formed between these new analogues and their DNA and RNA complementary strands were determined and compared with those of the corresponding unmodified oligonucleotides, as well as of the phosphorothioate and methylphosphonate derivatives. Dodecathymidines containing P-NH2 links form less stable duplexes with DNA targets, d(C2A12C2) (deltaTm/modification -1.4 degrees C) and poly dA (deltaTm/modification -1.1 degrees C) than the corresponding phosphodiester and methylphosphonate analogues, but the hybrids are slightly more stable than the one obtained with phosphorothioate derivative. The destabilization is more pronounced with poly rA as the target (deltaTm/modification -3 degrees C) and could be compared with that found with the dodecathymidine methylphosphonate. The modification is less destabilizing in an heteropolymer-RNA duplex (deltaTm/modification -2 degrees C). As expected, the P-NH2 modifications are highly resistant towards the action of various nucleases. It is also demonstrated that an all P-NH2 oligothymidine does not elicit Escherichia coli RNase H hydrolysis of the poly rA target but that the modification may be exploited in chimeric oligonucleotides combining P-NH2 sections with a central phosphodiester section.

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Section: Base-pairing Of Oligonucleotide Analogues With Dna and Rna C...supporting

confidence: 88%

Section: Introductionmentioning

confidence: 99%

Oligodeoxynucleoside phosphoramidates (P-NH2): synthesis and thermal stability of duplexes with DNA and RNA targets

Peyrottes

1996

Nucleic Acids Research

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“…Ce comportement est liC a une dCcomposition en milieu acide, qui vient d'etre Cgalement signalCe dans le cas de OPMe(NMe&, 23, et de 0PMe2NMe2, mais en solution dans NM (37). Pour notre part, afin de mettre en Cvidence cette dCcomposition, nous avons effectuC des dosages en retour par une solution de base forte (pipkridine) dans SIB.…”

Section: Dosage De Compose's Instables En Milieu Acideunclassified

“…Nous avons ici la preuve de la dCcomposition du produit initial (Fig. 5, courbes a, a'), ce qui est en accord avec les rCsultats rCcents de Matrosov et al (37); Lelikvre et Plichon (20) ---------I Nous retrouvons le m&me phCnomene de dCcomposition pour les dCrivCs azCtidinylCs 17, 18 et 19 (cf. courbes bb', Fig.…”

Section: Dosage De Compose's Instables En Milieu Acideunclassified

Basicité et structure de phosphoramides aliphatiques: dosage protométrique en solvants non-aqueux

Bollinger¹,

Faure²,

Yvernault³

1983

Can. J. Chem.

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Brönsted basicities (as half-neutralization potentials) have been determined at 25 °C by potentiometric titrations in nitromethane or in the mixture sulfolane/benzene 98:2 p/p for 19 aliphatic phosphoramides OPXYZ, with X, Y, or Z = Me; OEt; NMe2; NEt2; NHEt; N(CH2)n (n = 3 or 4); or X + Y = —NMe—(CH2)2—NMe—. Almost all of these weak bases give an homohydrogen bonding. Those with an Me or N(CH2)3 substituent are not stable in acidic medium, which is confirmed by back-titration and measure of E vs. time at the equivalent point. After comparing the results obtained in the two solvents, the effect of the nature of the substituents X, Y, Z on half-neutralization potentials and instability in acidic medium is analyzed.

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“…Attempts to employ a triflic acid catalyst as described by Klumpp with coworkers for N ‐(4,4‐diethoxybutyl)ureas and aminoacetals also failed and no cyclization products were observed in the reaction mixtures. This may be attributed to the protonation of amidophosphoryl moiety by superacid, which lowers the nucleophilicity of the nitrogen atom and hinders the cyclization.…”

Section: Methodsmentioning

confidence: 99%

2‐(Het)aryl‐N‐phosphorylpyrrolidines via Cyclization of Phosphorus Acid Amides: A Regioselective Approach

et al. 2020

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A first successful synthesis of 2-(het)aryl-N-phosphorylpyrrolidines is reported starting from readily available N-(4,4-diethoxybutyl)amides of P(V) acids. A range of phenols and hydroxyl-substituted O-heterocycles may be employed into the reaction furnishing N-phosphorylated 2-(het)arylpyrrolidines with up to 90 % yield. The developed method permits a presence of sensitive to phosphorylation hydroxy groups and provides the easy and regioselective entry to target compounds. Pyrrolidine core is widespread in natural products [1,2] and synthetic drugs. [3] Phosphorus-containing pyrrolidine derivatives are of a special interest due to their various biological [4-8] and catalytic [9,10] properties. Among them, (pyrrolidin-1-yl) phosphoramidates are proposed for hepatitis C, [11] malaria and tuberculosis [12] treatment, possess anti-HIV [13-16] and antitumor [17,18] activity. Additionally, they employed as chiral ligands in various asymmetric reactions. Examples are metal-catalyzed stereoselective reduction of ketones, [19,20] ketimines [21] and alkenes, [22-24] various cycloadditions, [25-29] addition of boronic acids [30] and organotrifluoroborates [31] to alkenes, asymmetric ruthenium-catalyzed metallo-ene reaction [32] and Suzuki-Miyaura coupling. [33]

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Phosphoric, Phosphonic, and Phosphinic Acid Amides as Bases

Cited by 7 publications

References 1 publication

Oligodeoxynucleoside phosphoramidates (P-NH2): synthesis and thermal stability of duplexes with DNA and RNA targets

Oligodeoxynucleoside phosphoramidates (P-NH2): synthesis and thermal stability of duplexes with DNA and RNA targets

Basicité et structure de phosphoramides aliphatiques: dosage protométrique en solvants non-aqueux

2‐(Het)aryl‐N‐phosphorylpyrrolidines via Cyclization of Phosphorus Acid Amides: A Regioselective Approach

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