Preparation of alkyl- and aryl-amino[<sup>2</sup>H<sub>2</sub>]methylphosphinic acids

Berté-Verrando, Sylvie; Nief, François; Patois, Carl; Savignac, Philippe

doi:10.1039/p19950002045

Cited by 6 publications

(4 citation statements)

References 10 publications

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“…These problems may be overcome if it is replaced by POCl 3 being used as solvent and reagent. [44][45][46][47]91,92] Only one of the chlorines of this reagent is used in the phosphonate-phosphonochloridate conversion and the monochlorination reactions render it a safe and convenient substitute to PCl 5 . The by-product is one equivalent of the corresponding alkyl dichlorophosphate 30 (Scheme 17).…”

Section: Scheme 15mentioning

confidence: 99%

Phosphonate–phosphonochloridate conversion

Iorga¹,

Carmichael²,

Savignac³

2000

Comptes Rendus de l'Académie des Sciences - Series IIC - Chemis

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This review deals with the phosphonate-phosphonochloridate conversion. The different phosphorus-chlorine bond forming reagents (COCl 2 , (COCl) 2 , SOCl 2 , PCl 5 , POCl 3 , Ph 3 PCl 2 , trichloro(o-phenylenedioxy)phosphorane) and the reaction conditions which they impose are considered. Phosphonates / Phosphonochloridates / Chlorinating Agents Version française abrégée -Conversion des dialkyl alkylphosphonates en alkyl chloroalkylphosphonates. La transformation des alkylphosphonates en chloroalkylphosphonates est une réaction très utile en chimie du phosphore. Les chloroalkylphosphonates sont de précieux intermédiaires dans la préparation de dérivés phosphorés plus élaborés tels que, fluoroalkylphosphonates, diesters mixtes, phosphoramideester, thiophosphonates et phosphinates. Plusieurs agents de chloration ont été introduits pour réaliser cette transformation: le phosgène, COCl 2 , le chlorure d'oxalyle, (COCl) 2 , le chlorure de thionyle, SOCl 2 , le pentachlorure de phosphore, PCl 5 , l'oxychlorure de phosphore, POCl 3 , Ph 3 PCl 2 et le trichloro(ο-phenylenedioxy)phosphorane. Les avantages et inconvénients de chaque réactif sont examinés en fonction des critères suivants: disponibilité, efficacité, tolérance, conditions d'emploi, solvant, température, nature des sous-produits. Trois réactifs se détachent, le chlorure d'oxalyle, le pentachlorure et l'oxychlorure de phosphore. Ils réalisent la transformation alkylphosphonates-chloroalkylphosphonates avec efficacité dans des conditions non destructrices et avec des phosphonates d'une grande variété structurale.

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Section: Scheme 15mentioning

confidence: 99%

Phosphonate–phosphonochloridate conversion

Iorga¹,

Carmichael²,

Savignac³

2000

Comptes Rendus de l'Académie des Sciences - Series IIC - Chemis

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“…These compounds are easily obtained using the Abramov reaction 7 and its modifications, 8 giving access to the synthesis of different types of α-functionalized phosphonates. 9 …”

Section: Introductionmentioning

confidence: 99%

Functionalization of α-hydroxyphosphonates as a convenient route toN-tosyl-α-aminophosphonates

et al. 2018

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Direct conversion of the a-hydroxyl group by para-toluenesulfonamide to yield a-(N-tosyl)aminophosphonates is reported. a-Aminophosphonates 23a,b-37a,b were obtained from the corresponding a-hydroxyphosphonates 6a,b-21a,b in the presence of K 2 CO 3 , via the retro-Abramov reaction of the appropriate aldehydes, 1-5. The subsequent formation of imines with simultaneous addition of diethyl phosphite provided access to the a-sulfonamide phosphonates 23a,b-37a,b with better diastereoselectivity than in the case of the Pudovik reaction. The mechanism for this transformation is proposed herein. When Cbz N-protected aziridine 9a,b and phenylalanine analogue 12a,b were exploited, intramolecular substitution was observed, leading to the corresponding epoxide 38 as the sole product, or oxazolidin-2-one 39 as a minor product. Analogous substitution was not observed in the case of proline 18a,b and serine 21a,b derivatives.

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“…Concurrently, an effective protocol for the synthesis of 2,2,2-trifluoroethyl azido (alkyl/aryl)[ 2 H 2 ]methylphosphinates 48a-d [49] has been developed, starting from the 2,2,2-trifluoroethyl chloro(alkyl/aryl) [ Thus, as shown in Scheme 19, treatment of the chlorophosphinates 47a-d with sodium azide in DMSO at 90 o C afforded azides 48a-d in good yields. Also here, crude azides 48a-d containing less than 8% of the side products were subjected to reduction to the corresponding aminophosphinates.…”

Section: Nucleophilic Substitution Of -Halogeno Derivativesmentioning

confidence: 99%

“…This process can be extended to the synthesis of 1-aminocycloalkylphosphonates [59], -hydroxy functionalized aminophosphonates [31][32][33], aminodideuteriomethylphosphonates or -phosphinates [46,49,62] and 1-amino-1-deoxy-1-phosphylglycerols [37].…”

Section: -Aminoalkylphosphonates and -Phosphinatesmentioning

confidence: 99%

Synthesis and Reactivity of Azidoalkylphosphonates, -Phosphinates and -Phosphine Oxides

Gajda

2007

COC

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This review will focus on the synthesis of -and -azidoalkylphosphonic and -phosphinic acids, -phosphine oxides and their derivatives as well as their reactions utilizing the azido group and/or phosphyl group. In the first part of this review synthetic routes to such azides will be reviewed. Generally, these compounds are achieved via nucleophilic substitution of hydroxy derivatives of phosphonates, -phosphinates, and -phosphine oxides by the Mitsunobu protocol or by the displacement of their sulfonates or halogen derivatives with azides. The ring-opening of phosphorus-containing oxiranes or cyclic vicinal sulfates with azides will also be discussed. Electrophilic azidation of the corresponding phosphorus-stabilized carbanions has also been described. In the second part of the review emphasis will be placed on the application of azido derivatives in organic synthesis. 1,3-Dipolar cycloaddition is an excellent tool in the construction of fivemembered heterocycles. Therefore, the formation of 1,2,3-triazoles from alkynes, enamines and 2-oxoalkylidenetriphenylphosphoranes will be discussed. Hence, the azido group is easily converted into amine, and phosphorus-containing azides can be considered to be azide-masked equivalents of amino derivatives or their N-protected derivatives. The application of such azides in the synthesis of phosphorus analogs of amino acids will be discussed. The synthesis of carbodiimides, imines, isothiocyanates and phosphonodipeptides has also been reviewed.

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Preparation of alkyl- and aryl-amino[²H₂]methylphosphinic acids

Cited by 6 publications

References 10 publications

Phosphonate–phosphonochloridate conversion

Phosphonate–phosphonochloridate conversion

Functionalization of α-hydroxyphosphonates as a convenient route toN-tosyl-α-aminophosphonates

Synthesis and Reactivity of Azidoalkylphosphonates, -Phosphinates and -Phosphine Oxides

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Preparation of alkyl- and aryl-amino[2H2]methylphosphinic acids

Cited by 6 publications

References 10 publications

Phosphonate–phosphonochloridate conversion

Phosphonate–phosphonochloridate conversion

Functionalization of α-hydroxyphosphonates as a convenient route toN-tosyl-α-aminophosphonates

Synthesis and Reactivity of Azidoalkylphosphonates, -Phosphinates and -Phosphine Oxides

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Preparation of alkyl- and aryl-amino[²H₂]methylphosphinic acids