Catalytic enantioselective Michael addition in the synthesis of α-aminophosphonates

Jászay, Zsuzsa M.; Németh, Gábor; Pham, Truong Son; Petneházy, Imre; Grűn, Alajos; Tőke, Lásʐló

doi:10.1016/j.tetasy.2005.10.020

Cited by 38 publications

(12 citation statements)

References 21 publications

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“…Hydrolysis of 22 by a weak acid resulted in a cyclic phosphonate (20a'), which could be further hydrolyzed by means of a strong acid to optically active phosphonoglutaminic acid (20a), a biologically active P-analogue of glutaminic acid. The absolute configuration of 20a was found to be S by comparison of the signs of optical rotation with literature value [61].…”

Section: Catalytic Enantioselective Synthesis Of α-And β-Aminophosphomentioning

confidence: 59%

Synthesis and Application of New, Optically Active Compounds as Catalysts and Ligands in Enantioselective Reactions

Mátravölgyi¹,

Kovács²,

Hegedűs³

et al. 2015

Period. Polytech. Chem. Eng.

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Section: Catalytic Enantioselective Synthesis Of α-And β-Aminophosphomentioning

confidence: 59%

Synthesis and Application of New, Optically Active Compounds as Catalysts and Ligands in Enantioselective Reactions

Mátravölgyi¹,

Kovács²,

Hegedűs³

et al. 2015

Period. Polytech. Chem. Eng.

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“…TADDOLates were also successfully employed for the asymmetric phase-transfer catalysed Michael addition of aminophosphonate 49 to acrylate 50 (Scheme 13) as shown by Jaszay et al28 After testing of a variety of different catalysts and conditions, the standard TADDOL 2c in combination with t BuONa as the base was identified as the best-suited chiral base, affording the product 51 in high yield and with reasonable enantioselectivity under cryogenic conditions. Unfortunately, the use of stoichiometric amounts of TADDOL was necessary to ensure high selectivities, with use of a catalytic amount only giving almost racemic product 28…”

Section: Chiral Phase-transfer Catalystsmentioning

confidence: 99%

Towards Tartaric‐Acid‐Derived Asymmetric Organocatalysts

2013

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Tartaric acid is one of the most prominent naturally occurring chiral compounds. Whereas its application in the production of chiral ligands for metal-catalysed reactions has been exhaustively investigated, its potential to provide new organocatalysts has been less extensively explored. Nevertheless, some impressive results, such as the use of TADDOLs as chiral H-bonding catalysts or of tartrate-derived asymmetric quaternary ammonium salt catalysts, have been reported over the last decade. The goal of this article is to provide a representative overview of the potential and the limitations of tartaric acid or TADDOLs in the creation of new organocatalysts and to highlight some of the most spectacular applications of these catalysts, as well as to summarize case studies in which other classes of chiral backbones were better suited.

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“…Recently, Jászay et al 128 reported the synthesis of ( S )-phosphoglutamic acid 200 via a catalytic enantioselective Michael addition. In this context, treatment of the achiral Schiff base 197 derived from phosphoglycine, with sodium tert -butoxide followed by the addition of tert -butyl acrylate in the presence of TADDOL 198 , produced the α-aminophosphonate 199 in 95% yield and 72% ee 129.…”

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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Catalytic enantioselective Michael addition in the synthesis of α-aminophosphonates

Cited by 38 publications

References 21 publications

Synthesis and Application of New, Optically Active Compounds as Catalysts and Ligands in Enantioselective Reactions

Synthesis and Application of New, Optically Active Compounds as Catalysts and Ligands in Enantioselective Reactions

Towards Tartaric‐Acid‐Derived Asymmetric Organocatalysts

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

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