Erythronic acid

Five pentosaccharinic acids were formed when D-xylose was treated with calcium hydroxide. This mixture included 2-C-methyl-D-threonic acid and 2-C-methyl-D-erythronic acid, the structures of which were... 

W. Pitsch, A. Russel, M. Zabel, and B. Konig, Synthesis of a functionalized cyclohepten-one from erythronic acid-4-lactone, Tetrahedron, 57 (2001) 2345-2347. 

The principle of the reactions between aldonolactones and HBr-HOAc is illustrated in Scheme 1 (entries I and II), and the mono- and di-bromodeoxylactones prepared in this way are listed in Table 1. The 2-bromo-2-deoxy-D-erythrono-and D-threonolactone can be prepared analogously to the L-isomers [11] from the salts of D-threonic and o-erythronic acid [ 12], respectively. The former can be prepared by oxidative degradation of D-xylose following an analogous procedure described by Humphlett [13]. 

Figure 9.8 Initial steps of the Maillard reaction with the formation of furosine (after hydrolysis with 7.8 M HCi) as well as of. Y-s-carboxymethyl lysine and erythronic acid (from Erbersdobler...

The best inhibitor is D-erythronic acid-4-phosphate (Compound 25, Table I), which has one less carbon than the normal substrate. This is very similar to the inhibitor-substrate... 

The alditol phosphate analogue of D-arabinose-5-phos-phate was a 3-fold less potent inhibitor than D-erythronic acid-... 

L-erythronic acids, respectively, and D-xylose to D-threonic acid.44 Isbell et al. elucidated the mechanism of this process45 (see the following Chapter). Degradation to a lower aldonic acid can be achieved by oxidation of an unsaturated sugar derivative. The method of Reichstein et al.46 for the preparation of L-threono-1,4-lactone by permanganate oxidation of 5,6-0-isopropylidene-L-ascorbic acid was improved by Perel and Dayton to afford the crystalline lactone in 65% yield.47... 

Ishizu et al.29H found that D-xylose and D-fructose react with aqueous calcium hydroxide to produce 13 lactonizable saccharinic and other acids. These were identified after separation by cellulose column and gas-liquid chromatography, and the Cs-saccharinic acids, 2-C-methyl-D-threonic acid (117) and 2-C-methyl-D-erythronic acid (118), were among those isolated. These authors299 later reported that L-sorbose reacts similarly, to generate 14 lactones, including the 2-C-methyl-L-xr/o o-l,4-lactone and 2-C-methyl-L-lyxono-1,4-lactone, which were also prepared from 1-deoxy-L-threo-pentulose via the cyanohydrin reaction. 

The aqueous oxidation of D-[l-14C]glucose and D-[6-14C]glucose at 100 °C afforded formic, acetic, and glycolic acids, and carbon dioxide. The last is mainly produced from C-2 to C-5, the formic acid from C-l, and the acetic acid from C-6.96 Addition of aluminum(III) chloride greatly increased the yield of carbon dioxide. Oxidation of D-glucose and D-fructose, studied with lsO-enriched oxygen, showed that they decompose via the C-l and C-2 hydroperoxides to give D-erythronic acid as the main product.76... 

At low temperatures, D-glucose and D-fructose in the presence of ferrous sulfate are converted into D-uru/u770-hexos-2-ulose (36), which can be degraded by further oxidation to glycolic acid, glyoxylic acid, and D-erythronic acid. The nature of the products formed under various conditions and the mechanism of the reaction have been described (see Ref. 1, p. 1133). In dilute solution, in the presence of ferrous sulfate at low temperature, compound 36 gave D-ura mo-2-hexulosonic acid (37) and D-ery//zro-hexo-2,3-diulosonic acid (38). In concentrated solutions, formaldehyde was also found. The formation of these products at low temperature was ascribed to the series of reactions in Scheme 19. 

At higher temperatures, carbon dioxide, formic acid, oxalic acid, glycolic acid, hydroxymalonic acid, glyceric acid, and other acids were shown to be formed. The formation of carbon dioxide is ascribed to decarboxylation of 38 oxalic acid and D-erythronic acid arise from cleavage of the C-2-C-3 bond compound 39 is cleaved to glyoxylic acid plus D-erythronic acid. Compound 40 is oxidized further to D-g7ycero-2,3-pentodiulosonic acid and is subsequently cleaved to oxalic and glyceric acids. 

D-Erythrofuranoside, l-(D-gIucopyrano-syl)-, IV, 139, 148 hexaacetate, IV, 148 D-Erythronamide, 2,4-dimethyl-, III, 165 D-Erythronic acid, 3-methyl-, II, 100 L-Erythronic acid, and brucine salt, III, 144... 

Isopropy11dene-0-erythronolactone Erythronic acid, 2,3-0-1so-propylidene-y-lactone, D- (8) Furo[3,4-d]-l, 3-d1oxol-4(3aH)-one, dihydro-2,2-dimethyl-, (3aR-cis)- (9) (2SS81-41-3)... 

Fig. 8-15. Possible carboxyl group structures formed in cellulose during chlorine and hypochlorite stages. 1, Arabinonic acid 2, erythronic acid 3, glucuronic acid 4, dicarboxylic acid.

Fig. 8-18. Oxidative stabilization of cellulose through formation of aldonic acid end groups. R is cellulose chain. After oxidative formation of a glucosone intermediate this undergoes a benzilic acid rearrangement strongly favoring formation of mannonic acid end groups (2). In addition, cleavage of C-1 to C-2 and C-2 to C-3 bonds gives rise to the formation of arabinonic acid (3) and erythronic acid (4) end groups. (In this simplified scheme only the main products are shown.)...

Amino-4-deoxy-2,3-0-isopropylidene-D-erythronic acid (155), obtainable from the lactone derivative 153 by treatment with sodium azide followed by hydrogenation of the azido acid (154), forms the lactam (156), but only on sublimation at 150°, because the elements of water must be removed thermally. Once formed, the sterically favored, five-membered lactam (156) is stable toward hydrolysis by acid, in contrast to the six-membered D-ribonolactam (151), and the isopropylidene group can be removed with acid, to give free 4-amino-4-deoxy-D-erythronolactam. 

---