2-aminoethylphosphonate

Aminoethylphosphonate.—n.m.r. measurements indicate that 78% of the phosphorus present in a water-soluble glycoprotein from the sea anemone Metridium dianthus is in the phosphonate form and includes 2-aminoethyl-phosphonic acid (20). N.m.r. for the identification of naturally occurring phosphonates appears to be a technique superior to chromatography, which has been used hitherto.  

The structure of a ceramide aminoethylphosphonate from Metridium senile has been shown to be (21). Hydrolysis of (21) by phospholipase gave (20) which was identified by g.l.c. and mass spectrometry. The ceramide fraction after this hydrolysis was itself hydrolysed by alkali, and the fatty acids together with the long-chain bases were also identified by g.l.c.-m.s. The composition of the long-chain bases was found to differ between anemones captured in April and in August the former lacked sphingosine. 

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C1SH19NO2 47017-04-9) see Metaraminol a-aminoethylphosphonic acid diethyl ester... 

A. Aminophosphonic Acids.— The Michael addition of a dialkyl phosphite to acrylonitrile leads to C—P bond formation and the production in high yield of derivatives of 2-aminoethylphosphonic acid (45). This synthetic method appears to be preferable to those already described. ... 

The phosphonatase (hydrolase) pathway is less widely used, typically for the degradation of 2-aminoethylphosphonate via phosphonoacetaldehyde to acetaldehyde, and the degradation of phosphonoacetate that involves a specific hydrolase (Kulakova et al. 2001). 

La Nauze JM, H Rosenberg (1968) The identification of 2-phosphonoacetaldehyde as an intermediate in the degradation of 2-aminoethylphosphonate by Bacillus cereus. Biochim Biophys Acta 165 438-447. 

Ternan NG, JP Quinn (1998) Phosphate starvation-independent 2-aminoethylphosphonic acid biodegradation in a newly isolated strain of Pseudomonas putida, NG2. System Appl Microbiol 21 346-352. 

A new synthesis (Scheme 4) of 2-aminoethylphosphonic acid (24) has been described in which bis(dimethylamino) phosphorochloridate is condensed with an a-anion derived from an aliphatic nitrile.71 An advantage of this synthesis is that the intermediate (25) can be alkylated, which constitutes the simplest synthesis so far published for substituted aminoethylphosphonic acids. Both C-3 and the phosphorus atom of PEP are incorporated into (24) in Tetrahymena pyriformis,72 which confirms... 

Subsequent reduction of the alkylated cyanomethylphosphonates produces p-aminoethylphosphonates. Diethyl aminomethylphosphonates are C-alkylated with a range of agents via the initial formation of the imines [73],... 

Fig. 5. The reaction of ethanolamine-phosphate cytidylytransferase with substrates and analogues. Reaction 1 shows the normal reaction of the enzyme with ethanolamine phosphate (2-aminoethyl phosphate), which is part of the route of phospholipid synthesis. The alternative reaction with 2-aminoethylphosphonate, in parentheses, is used by some marine organisms to insert a C—P bond into their phospholipids. Reaction 2 shows the futile cycle obtained with 2-aminoethylarsonate (59). The symbol -P signifies -P03H2 and its ionized forms, and -P- signifies -P(0)(0H)- and its ionized form (61).

The lipids of some organisms, such as Tetrahymena, contain aminoethylphosphonate, a compound with a C-P bond (Chapter 8). There are also many other naturally occurring phosphono compounds and huge quantities of synthetic phosphonates, present in detergents, herbicides, and insecticides, are metabolized by bacteria 297 Here we will consider only one step in the biosynthesis of phosphonates, the conversion of PEP into phosphonopyruvate (Eq. 13-54), a reaction catalyzed by PEP mutase. The phospho group is moved... 

Before 1975, peptides with C-terminal l-aminoalkylphosphonic acid residues (1-APA) or their esters 1 were essentially unknown. In 1978, the antibacterial properties of phospho-nopeptides incorporating C-terminal 1-aminoethylphosphonic and aminomethylphosphonic acids were reported1 1 and this stimulated interest in this class of compounds. Alaphosphalin [2, alaphosphin, l-(L-alanylamino)ethylphosphonic acid] is probably the first example of a rationally designed synthetic antibiotic. Alaphosphalin did not reach the market, however its discovery increased interest in the development of new synthetic methods for the synthesis of l-aminoalkylphosphonic adds as well as their esters and peptides. 

Aminoalkylphosphonic acids are analogues of natural a-aminocarboxylic acids and are designated by generally accepted three-letter abbreviations for the amino acid residue followed by a superscript P. For example, 1-aminoethylphosphonic acid, which is related to alanine, is abbreviated as Alap. Diphenyl [l-(benzyloxycarbonylamino)ethyl]phosphonate, is abbreviated as Z-Alap(OPh)2. The l-aminoalkylphosphonic acids have modest water solubility, which significantly increases in strong acidic and alkali solution. They are not soluble... 

A few methods for the esterification of 1-aminoalkylphosphonic adds have been developed for use when diesters of 1-aminoalkylphosphonic acids are the preferred starting materials for peptide synthesis. 8 In general, 1-aminoalkylphosphonic acids cannot be esterified under conditions that work for amino acids, and protection of the amino group is absolutely essential. Diethyl 1-aminoethylphosphonate [9, Alap(OEt)2] is synthesized from Alap in two steps (Scheme 6). Orthoformates are highly recommended because esterification is almost quantitative. 24 ... 

Scheme 6 Synthesis of Diethyl 1-Aminoethylphosphonate from 1-Aminoethylphosphonic Acid1241...

As seen in Scheme 1 a route similar to the biological pathway has now been explored by the independent synthesis of each precursors by chemical means. Work presented in this communication describes the production of synthetic 2-aminoethylphosphonic acids by the controlled reductive amination of 2-oxoalkylphosphonate diesters... 

N-Hydroxysuccinimide ester of N-benzyloxycarbonyl-L-alanine (lR,S)-l-Aminoethylphosphonic acid Benzylamine Palladium on carbon... 

A representative sphingophosphonolipid in which the aminoethylphosphonate head group may contain a hydroxy group (R = OH) or a N-methyl group (R" = CH3)... 

Figure 3 The structures of sphingomyelin (1), ceramide aminoethylphosphonate (2), and inositol phosphorylceramide (InsPCer) (3).

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