Pyruvic acid amides

The catalytic hydrogenation of the benzoylformic acid amides of optically active amino acid esters was carried out. When the (5)-amino acid ester was used, the resulting mandelic acid had the (R)-con-figuration. When pyruvic acid amides of optically active benzylic amines were hydrogenated over palladium, optically active lactic acid was obtained in relatively high enantiomeric excess (ee 60%). The... 

In the sequel, we will discuss a generalization of the chelation hypothesis as it applies to reactions other than hydrogenation of Schiff bases of a-keto acids with chiral amines. The catalytic hydrogenation of pyruvic acid amide resulted in the formation of lactcimide in high optical purity (75-99% diastereomeric excess)(] ). This might be explained by the chelate conformation of the substrate-catalyst complex shown in Scheme 8. 

Acetamidoxime 0-Formyl, in A-00004 Methylglyoxime, in P-00446 Pyruvic acid Amide, oxime, in P-00448... 

Methylindole has been prepared from the a5-methylphenyl-hydrazone of pyruvic acid, by the action of sodium amide or sodium hydride on indole followed by methyl iodide at elevated temperatures,by treatment of indole with methyl p-toluene-sulfonatc and anhydrous sodium carbonate in boiling xylene, and by the action of inelhyl sulfate on indole previously treated... 

For the third pair of alkaloids, ergosine and ergosinine, the latter was shown by Smith and Timmis to yield lysergic acid (or its amide, eigine), pyruvic acid and Meucine, while on distillation under reduced pressure it furnished a product, C11H18O2N2, m.p. 148°, -f-105° (c = 1, H2O),... 

Recently, Borner and coworkers described an efficient Rh-deguphos catalyst for the reductive amination of a-keto acids with benzyl amine. E.e.-values up to 98% were obtained for the reaction of phenyl pyruvic acid and PhCH2COCOOH (entry 4.9), albeit with often incomplete conversion and low TOFs. Similar results were also obtained for several other a-keto acids, and also with ligands such as norphos and chiraphos. An interesting variant for the preparation of a-amino acid derivatives is the one-pot preparation of aromatic a-(N-cyclohexyla-mino) amides from the corresponding aryl iodide, cyclohexylamine under a H2/ CO atmosphere catalyzed by Pd-duphos or Pd-Trost ligands [50]. Yields and ee-values were in the order of 30-50% and 90 >99%, respectively, and a catalyst loading of around 4% was necessary. 

A few enzymes that might be expected to have PLP at their active sites have instead a prosthetic group consisting of pyruvic acid bound by an amide linkage, a pyruvoyl group (Table 14-4). These and ... 

Oxidation of SeC 144 derivatives also generates AAla derivatives. Hoffmann degradation of u,p-diaminopropanoic acid, 145 Bergmann s re action11461 of condensation of amides with pyruvic acid, N-hydroxylation followed by dehydration, 147 and N-chlorination/dehydro-chlorination 122-124 have also been used for the synthesis of AAla derivatives. 

Oxazolidinones are the products of the acid-catalyzed condensation of a-hydroxyamides with aldehydes and ketones (equation 178). Tertiary amides derived from pyruvic acid undergo intramolecular cyclization when irradiated (equation 179) (78JOC419). Treatment of the a-bromo amide (308) with sodium hydride yields inter alia the dimeric oxazolidinone (309), presumably by way of an a-lactam, which adds to the carbonyl group of a second molecule of the amide (equation 180) (80JCS(P1)2249). 

Bleyer and Braun oxidized D-glucose with chloramine in alkali under these conditions the chloramine was converted to the amide and sodium hypochlorite, the action of the latter being very drastic. Each mole of aldose consumed 8 equivalents of oxygen, liberated 2 moles of carbon dioxide and formed 2 equivalents of an unknown acid. The reaction went more rapidly as the alkalinity was increased. The acid was assumed to be acetic acid, formed from pyruvic acid D-gluconic acid was considered to be the primary oxidation product. Bernhauer and... 

The unsaturated products (dehydropeptides) of Equations 2 and 3 are labile and readily hydrolyze to yield amide plus pyruvic acid and acetaldehyde respectively (11)... 

The various reactions characteristic of an alcohol which lactic acid (or it esters or amides) may undergo are xanthation with carbon bisulphide, esterification with organic acids and dehdrogenation or oxygenation to form pyruvic acid or its derivatives. The acid reactions of lactic acid are those that form salts. It also imdergoes esterification with various alcohols. 

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