Phosphinothricins synthesis

Maier, L. and Rist, G., Organic phosphorus compounds. 77. Synthesis and properties of phosphinothricin homologs and analogs, Phosph. Sulf, 17, 21, 1983. 

Zeiss, H.J., Enantioselective synthesis of L-phosphinothricin. III. Enantio-selective synthesis of L-phosphinothricin from L-methionine and L-glutamic acid via L-vinylglycine, Tetrahedron, 48, 8263, 1992. 

Both (R)- and (S)-amino transferase are available forthe synthesis of enantiomerically pure amines from racemic amines. Degrees of conversion were at or close to 50% for resolutions, and enantioselectivities customarily reached > 99% e.e. for the amine product from both resolutions or syntheses from ketones (Stirling, 1992 Matcham, 1996). The donor for resolutions of amine racemates was usually pyruvate whereas either isopropylamine or 2-aminobutane served as donors for reduction of ketones. The products range from i- and D-amino acids such as i-aminobutyric acid (see Section 7.2.2.6) and i-phosphinothricin (see Section 7.4.2) to amines such as (S)-MOIPA (see Section 7.4.2). 

L Berlicki, A Obojska, G Forlani, P Kafarski (2005) Design, Synthesis, and Activity of Analogues of Phosphinothricin as Inhibitors of Glutamine Synthetase, J Med Chem 48(20) 6340-6349... 

Many other phytotoxins not presented here have been structurally characterized and tested In some plant bioassay systems. Numerous other reported phytotoxin studies are In the "active fraction" stage and structure elucidation of the active components has not been achieved. Nevertheless, from the data presented. It can generally be concluded that diverse microbes produce a broad range of chemistries with phytotoxic activities chemical and biochemical synthesis of almost all of these compounds Is unknown (but derivitizatlon studies to alter phytotoxic activity have been used In a few Instances) knowledge of the spectrum of species susceptible to these compounds Is Incomplete (many weed and crop species have not been tested some compounds are toxic to organisms other than plants) and the molecular mode of phytotoxin action Is unstudied or unknown for most. The major exception Is the vast amount of data on blalaphos, phosalacine, and phosphinothricin, which have achieved commercial status. 

Minowa, N., Huayama, M., and Fukatsu, S., Asymmetric synthesis of (-i-)-phosphinothricin and related compounds by the Michael addition of glycine Schiff bases to vinyl compounds. Bull. Chem. Soc. Jpn., 60, 1761, 1987. 

Logusch, E.W., Facile synthesis of D,L-phosphinothricin from methyl 4-bromo-2-phthalimidobutyrate, Tetrahedron Lett., Tl, 5935, 1986. 

Wasielewski, C., and Antezak, K., Aminophosphonic acids. Part 16. A new and facile synthesis of phosphinothricine and 2-amino-4-phosphonobutanoic acid, Synthesis. 540, 1981. 

A highly novel approach to the synthesis of glufosinate (phosphinothricin) consists in the amidocarbonylation of esters of methylvinylphosphinic acid (294) and followed from a study of the simple carbonylation of the same acid esters in the presence of one of a series of metal carbonyl complexes. In the presence of [Co2(CO)g], a mixture of hydrogen and carbon monoxide at 140 atm adds to the acid in the presence of benzamide in thf at 120 °C to give the product, mainly as the fully esterified compound, 295, together with small amounts of free amino acid ... 

Alternatively, the use of acetamidomalonic ester in the classical manner is exemplified by the synthesis of 2-amino-7,7-difluoro-7-(dihydroxyphosphinoyl)heptanoic acid (Scheme 32) in the search for compounds with NMDA antagonist activity, and in yet another synthesis of phosphinothricin. ... 

Leuckart-like reactions have been noted for the co-phosphinoylalkanals 304 and related compounds In these reactions, and also for those with analogous ketones the carbonyl reactant is subjected to reductive amination with ammonia (as ammonium acetate) or amines and NaBH3CN in MeOH at pH 7-7.5 the process is very sensitive to steric hindrance and probably proceeds via an enaminophonate intermediate. The sequence is illustrated (Scheme 38) by a direct synthesis of racemic phosphinothricin, but the involvement of the optically active 1,2-azaphospholidine 118 led to an optically active product ". ... 

The hydroformylation and amidocarbonylation of esters of methylvinylphosphinic acid have been studied in relation to the synthesis of probably the best known molecule t)f the types under consideration, viz. 2-amino-4-(hydroxymethylphosphinyl)butanoic acid, (398), also known as phosphinothricin or glufosinate. The outcome of the hydroformylation of the ester (401) depends on the nature of the catalyst employed. Thus the u.se of Rh (CO)j2. Rh2Cl2(CO)4, or HRh(CO)(PPh )2, leads to relatively high total yields of (402) and (403) but with low selectivity in contrast, when Co2(CO)j is employed, high selectivity with relatively low total yields are observed. Reactions in methanol afford a 90% relative yield of (402), Subsequent amidocarbonylation using the... 

The key reaction in the synthesis of biological organophosphates is the formation of a C-P linkage by the phosphoenolpyruvate phosphonopyruvate mutase reaction [Fig. 3(A)]. The enzyme has been purified from Tetrahymena pyriformis [35]. The equilibrium of the reaction is far on the side of phosphoenolpyruvate, and is shifted towards phosphonopyruvate formation by subsequent decarboxylation of phosphonopyruvate to phosphonoacetaldehyde [36]. Further phosphoenolpyruvate mutase enzymes have been characterized in Trypanosoma cruzi [37] and Mytilus edulis [38]. Phosphonoacetaldehyde is the key compound from which the synthesis of phosphonoethanolamine and phosphonomycin proceeds. Biosynthesis of phosphinothricin starts with an analogous reaction... 

Meiji Seika obtains the tripeptide (Bialaphos) by fermentation and sells it under the trade name Herbiace . Hoechst developed a chemical synthesis for glufosinate (the diastereomeric mixture of phosphinothricin). The methylphos-phonite monoester serves as the key building, and is readily accessible by two routes ... 

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