Addition of amine derivatives to phosphorylated 1,2-diaza-1,3-butadienes. Synthesis of α-aminophosphonates

Palacios, Francisco; Aparicio, Domitila; López, Yago; Santos, Jesús M. de los

doi:10.1016/j.tetlet.2004.03.192

Cited by 25 publications

(10 citation statements)

References 34 publications

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“…For this reason, we explored the reaction with styrene. Highly coloured 4-phosphinyl-1,2-diaza-1,3-butadiene (2a; R = Ph), obtained as a mixture of the E-and Zisomers in a ratio of 85:15, was generated in situ from chlorohydrazones 1 (R = Ph, R 1 = Et) in the presence of triethylamine [15] (Scheme 1). Addition of styrene (3) to 1,2-diaza-1,3-butadiene 2a led to the formation of tetrahydropyridazylphosphane oxide (4a; R = Ph, R 1 = Et) in moderate yield (66 %) and in a regioselective fashion (Scheme 1).…”

Section: Resultsmentioning

confidence: 99%

“…Peaks are reported in cm -1 . Chlorohydrazones 1 [15] and 1,2-diaza-1,3-butadienes 2 [15] were synthesised according to literature procedures. Obtained as a white solid from 1a (0.38 g, 1 mmol) and 2,3-dihydrofuran 9 (2 mL) as described in the general procedure.…”

Section: Methodsmentioning

confidence: 99%

“…Recently, we described the preparation of new phosphorylated conjugated aza-alkenes [15] (IV, Figure 2) and the preparation of α-aminophosphorus derivatives (V, Figure 2) by Michael addition of amines to these substrates. As a continuation of our work on the cycloaddition reaction of azadienes [9] and on the preparation of phosphorussubstituted heterocycles, [11][12][13] here we aim to explore the behaviour of heterodienes, such as 4-phosphinyl-IV (R = Ph) and 4-phosphonyl 1,2-diaza-1,3-butadienes IV (R = OEt), towards olefins for the preparation of the phosphorus-substituted heterocycles (VI, Figure 2).…”

Section: Introductionmentioning

confidence: 99%

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Cycloaddition Reactions of Phosphorylated 1,2‐Diaza‐1,3‐butadienes with Olefins: Regioselective Synthesis of Pyridazine Derivatives

et al. 2005

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The aza‐Diels–Alder reaction of 4‐phosphinyl‐ and 4‐phosphonyl‐1,2‐diaza‐1,3‐butadienes with styrene, cyclopentadiene, dihydrofuran and norbornadiene is reported. Monocyclic, bicyclic and polycyclic tetrahydropyridazines containing a phosphane oxide or a phosphonate substituent are obtained. The formation of cycloadducts can be explained by an endo transition state in the cycloaddition process of these heterodienes with styrene, cyclopentadiene, dihydrofuran, and by means of an exo transition state in the case of norbornadiene. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)

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Section: Resultsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Cycloaddition Reactions of Phosphorylated 1,2‐Diaza‐1,3‐butadienes with Olefins: Regioselective Synthesis of Pyridazine Derivatives

et al. 2005

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“…Palacios et al 147 reported that the addition of ( R )-α-MBA (R = Me, R' = Ph) and ethyl ( S )-valinate (R = CO 2 Et, R' = i -Pr) to 1,2-diaza-1,3-butadiene 237 afforded the α-aminophosphonates 238 and 239 , respectively, in good yield but with very low diastereoselectivity (<10% ds), (Scheme 61). Similar results were obtained in the addition of non-chiral amines to 237 .…”

Section: Stereoselective Synthesis Of α-Aminophosphonic Acids and mentioning

confidence: 99%

An overview of stereoselective synthesis of α-aminophosphonic acids and derivatives

2009

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An overview of all methodologies published during the last few years focused to the stereoselective (diastereoselective or enantioselective) synthesis of α-aminophosphonic acids and derivatives is reported. The procedures have been classified according a retrosynthetic strategy and taking into account the formation of each one of the bonds connected to the chiral centre. Keywordsα-Aminophosphonic acids; α-Aminophosphonates; Stereoselective Synthesis; Resolution; Chiral Pool Introducciónα-Aminoalkylphosphonic acids 1 are structurally analogous to α-amino acids 2, obtained by isosteric substitution of planar and less bulky carboxylic acid (CO 2 H) by a tetrahedral phosphonic acid functionality (PO 3 H 2 ). Several aminophosphonic, aminophosphinic and aminophosphonous acids have been isolated from various natural sources either as free amino acids or as constituents of more complex molecules. 1 Many natural and synthetic aminophosphonic acids, their phosphonate esters and short peptides incorporating this unit, exhibit a variety of biological properties. 2 Their diverse applications include enzyme inhibitors 3 such as synthase, 4 HIV protease, 5 rennin, 6 phosphatasa activity, 7 PTPases, 8 and potent antibiotics, 9 as antibacterial agents, 10 antiviral, 11 antifungal, 12 herbicides, 13 antitumor agents. 14 Their role for antibody generation is also well documented. 15 In addition, the incorporation of cyclic amino acids of medium ring size into key positions in peptide chains plays an important role, and constitutes the most prominent pathway to conformationally constrained peptidomimetics, a tool in modern drug discovery. NIH-PA Author ManuscriptNIH-PA Author Manuscript NIH-PA Author ManuscriptIn addition, α-aminophosphonic acids and their monoalkyl esters are also of interest in hydrometallurgy in order to extract metals 17 and in diagnostic medicine as screening agents, once complexed with lanthanides and actinides. 18,19 It is well known that the biological activity of α-aminophosphonic acids and derivatives depends on the absolute configuration of the stereogenic α carbon to phosphorous. 20 For example, (R)-phospholeucine 3 is a more potent inhibitor of leucine aminopeptidase than the S enantiomer, 21 and (S,R)-alafosfalin 4 shows higher antibacterial activity against both Grampositive and Gram-negative microorganisms than the other three diastereoisomers. 22 In view of the different biological and chemical applications of the α-aminophosphonic acids and derivatives, in the last 35 years the development of suitable synthetic methodologies for their preparation in optically pure form has been a topic of great interest in several research groups. In this context, several protocols for efficient asymmetric synthesis of α-aminophosphonic acids and derivatives have emerged in the recent years and several reviews have been published. 23 Now we would like to report herein an update over stereoselective synthesis of α-aminophosphonic acids and derivatives from 1998-2007. The principal synthetic stra...

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“…[2][3][4] For this purpose, we first envisioned, without prior protection of the ketone moiety, [5][6] their deprotonation with an excess of strong bases including LDA and NaH then the trapping of the intermediate enolates with various electrophiles (alkyl, alkenyl or benzyl halides, bromine, and aldehydes). [7][8][9][10] Among these reactions, we intended to particularly develop the Wittig-Horner olefination using various aldehydes as electrophiles, which would afford a variety of 1,3-dienes that are employed as useful substrates in the reaction of Diels-Alder. 11 First, we attempted the deprotonation of the γ-keto allyl phosphonate 1a at 0 °C by NaH or LDA (1-6 equiv) in THF, followed by the addition of bromine (1-2 equiv) at room temperature then at reflux for 4 h. Unfortunately, the starting material 1a was completely recovered.…”

Section: Introductionmentioning

confidence: 99%

Chemoselective reaction of ethane-1,2-dithiol, hydrazines, and hydroxylamine onto γ-keto allyl phosphonates and phosphine oxides

Elleuch¹,

Baioui²,

Bouajila³

et al. 2017

Arkivoc

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Addition of amine derivatives to phosphorylated 1,2-diaza-1,3-butadienes. Synthesis of α-aminophosphonates

Cited by 25 publications

References 34 publications

Cycloaddition Reactions of Phosphorylated 1,2‐Diaza‐1,3‐butadienes with Olefins: Regioselective Synthesis of Pyridazine Derivatives

Cycloaddition Reactions of Phosphorylated 1,2‐Diaza‐1,3‐butadienes with Olefins: Regioselective Synthesis of Pyridazine Derivatives

An overview of stereoselective synthesis of α-aminophosphonic acids and derivatives

Chemoselective reaction of ethane-1,2-dithiol, hydrazines, and hydroxylamine onto γ-keto allyl phosphonates and phosphine oxides

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