1-( N -Acylamino)-1-triphenylphosphoniumalkylphosphonates: General synthesis and prospects for further synthetic applications

Kuźnik, Anna; Mazurkiewicz, Roman; Zięba, Magdalena; Erfurt, Karol

doi:10.1016/j.tetlet.2018.07.040

Cited by 8 publications

(15 citation statements)

References 12 publications

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“…The starting diethyl 1-( N -acylamino)-1-ethoxyalkylphosphonates ( Table 1 , 3a – n ) were synthesized according to a previously described two-step protocol with some modifications ( Scheme 2 ) [ 33 ]. The general procedure consists of acylation of the imidate hydrochloride 1 with an acyl chloride (Step 1) and the Michaelis–Becker-like addition of diethyl phosphite to ethyl N –acylimidate 2 (Step 2).…”

Section: Resultsmentioning

confidence: 99%

“…Step 1: N -Acylation reactions of ethyl imidate hydrochlorides 1 were carried out according to the modified procedure described by Kuźnik et al [ 33 ]. The appropriate base (17.6 mmol, 2.2 eq.)…”

Section: Methodsmentioning

confidence: 99%

“…To overcome this problem, we looked for a different method of obtaining α-alkoxy derivatives of diethyl α-aminophosphonates with the result of the development of another procedure for the preparation of diethyl 1-( N -acylamino)-1-ethoxyalkylphosphonates 3 obtained in a Michaelis–Becker-type reaction of ethyl N -acylimidates 2 with diethyl phosphite ( Scheme 1 , pathway b) [ 33 ]. This opened up the wider applicability of this method, since the electrochemical oxidation step required in the previous transformation is omitted in this case, while the starting N -acylimidates 2 are readily available from the well-known class of chemical compounds, i.e., ethyl imidate hydrochlorides 1 [ 34 , 35 ].…”

Section: Introductionmentioning

confidence: 99%

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One-Pot and Catalyst-Free Transformation of N-Protected 1-Amino-1-Ethoxyalkylphosphonates into Bisphosphonic Analogs of Protein and Non-Protein α-Amino Acids

et al. 2022

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Herein, we describe the development of one-pot transformation of α-ethoxy derivatives of phosphorus analogs of protein and non-protein α-amino acids into biologically important N-protected 1-aminobisphosphonates. The proposed strategy, based on the three-component reaction of 1-(N-acylamino)-1-ethoxyphosphonates with triphenylphosphonium tetrafluoroborate and triethyl phosphite, facilitates good to excellent yields under mild reaction conditions. The course of the reaction was monitored by 31P NMR spectroscopy, allowing the identification of probable intermediate species, thus making it possible to propose a reaction mechanism. In most cases, there is no need to use a catalyst to provide transformation efficiency, which increases its attractiveness both in economic and ecological terms. Furthermore, we demonstrate that the one-pot procedure can be successfully applied for the synthesis of structurally diverse N-protected bisphosphonic analogs of α-amino acids. As shown, the indirect formation of the corresponding phosphonium salt as a reactive intermediate during the conversion of 1-(N-acylamino)-1-ethoxyphosphonate into a 1-aminobisphosphonate derivative is a crucial component of the developed methodology.

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Section: Resultsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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One-Pot and Catalyst-Free Transformation of N-Protected 1-Amino-1-Ethoxyalkylphosphonates into Bisphosphonic Analogs of Protein and Non-Protein α-Amino Acids

et al. 2022

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“…Further research on phosphorus analogs of α-amino acids 37 revealed the possibility of transforming them into bisphosphoric acid esters 43 , which also exhibit important biological activity ( Scheme 13 ) [ 56 , 57 ].…”

Section: 1-aminoalkyltriarylphosphonium Derivativesmentioning

confidence: 99%

“…As shown, the high reactivity of the phosphonium salts 42 can be used not only in the α-amidoalkylation reactions of phosphorus or carbon nucleophiles ( Scheme 13 , route A and B) but also in the elimination ( Scheme 13 ; route C) or Wittig reaction ( Scheme 13 , route D) [ 57 ].…”

Section: 1-aminoalkyltriarylphosphonium Derivativesmentioning

confidence: 99%

1-Aminoalkylphosphonium Derivatives: Smart Synthetic Equivalents of N-Acyliminium-Type Cations, and Maybe Something More: A Review

et al. 2022

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N-acyliminium-type cations are examples of highly reactive intermediates that are willingly used in organic synthesis in intra- or intermolecular α-amidoalkylation reactions. They are usually generated in situ from their corresponding precursors in the presence of acidic catalysts (Brønsted or Lewis acids). In this context, 1-aminoalkyltriarylphosphonium derivatives deserve particular attention. The positively charged phosphonium moiety located in the immediate vicinity of the N-acyl group significantly facilitates Cα-P+ bond breaking, even without the use of catalyst. Moreover, minor structural modifications of 1-aminoalkyltriarylphosphonium derivatives make it possible to modulate their reactivity in a simple way. Therefore, these types of compounds can be considered as smart synthetic equivalents of N-acyliminium-type cations. This review intends to familiarize a wide audience with the unique properties of 1-aminoalkyltriarylphosphonium derivatives and encourage their wider use in organic synthesis. Hence, the most important methods for the preparation of 1-aminoalkyltriarylphosphonium salts, as well as the area of their potential synthetic utilization, are demonstrated. In particular, the structure–reactivity correlations for the phosphonium salts are discussed. It was shown that 1-aminoalkyltriarylphosphonium salts are not only an interesting alternative to other α-amidoalkylating agents but also can be used in such important transformations as the Wittig reaction or heterocyclizations. Finally, the prospects and limitations of their further applications in synthesis and medicinal chemistry were considered.

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Chemoselective Synthesis of α-Amino-α-cyanophosphonates by Reductive Gem-Cyanation–Phosphonylation of Secondary Amides

Chen¹,

Wang

Huang

2019

Org. Lett.

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A novel approach to α-amino-α-cyanophosphonates has been developed. The method features a Tf 2 O-mediated reductive geminal cyanation/phosphonylation of secondary amides. Mild reaction conditions, high bond-forming efficiency, inexpensive readily available starting materials, and good to excellent yields with wide functional group compatibility constitute the main advantages of this method. The protocol can be run on a gram scale.

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1-( N -Acylamino)-1-triphenylphosphoniumalkylphosphonates: General synthesis and prospects for further synthetic applications

Cited by 8 publications

References 12 publications

One-Pot and Catalyst-Free Transformation of N-Protected 1-Amino-1-Ethoxyalkylphosphonates into Bisphosphonic Analogs of Protein and Non-Protein α-Amino Acids

One-Pot and Catalyst-Free Transformation of N-Protected 1-Amino-1-Ethoxyalkylphosphonates into Bisphosphonic Analogs of Protein and Non-Protein α-Amino Acids

1-Aminoalkylphosphonium Derivatives: Smart Synthetic Equivalents of N-Acyliminium-Type Cations, and Maybe Something More: A Review

Chemoselective Synthesis of α-Amino-α-cyanophosphonates by Reductive Gem-Cyanation–Phosphonylation of Secondary Amides

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