Amadori reaction

Among the best known is that due to Hodges, with an Amadori reaction as the first reaction be-... 

We observed no release after reductive amination of the Schiff base. The release of the residual amounts of protein after its cross-linking, which amounted to up to 70 % (Fig. 17), may only occur upon biodegradation of complexes in vivo. It is also possible that Amadori reactions could lead to a permanent, covalent immobilization of a part of the entrapped protein, only capable of release under matrix breakdown conditions. 

Degradation Rearrangement Hydrolysis Double bond shift Ring transformation Ring-contraction Ring-expansion Ferrier carbocyclization Anomerization Aromatization Maillard reaction Amadori reaction... 

The Amadori product from D-glucose 33 and L-proline decomposes at 130 °C in DMF to afford 33 and D-Mannose 54, indicating the reversibility of the Amadori reaction. A kinetic study using 33 and phenylalanine indicates that the Schiff s base formation is the rate-determining step of the Maillard reaction [275,276]. 

The synthesis of novel DNA topoisomerase II (topo II) inhibitors was undertaken in the laboratory of T.L. MacdonaldJ" Their research program dealt with the synthesis of piperidin-3-one derivatives, which were needed as synthetic intermediates for a variety of potential topo ll-directed agents. The key step in their approach was the Amadori reaction for the preparation of highly functionalized piperidin-3-ones under mild conditions. Upon treatment with a catalytic amount of p-toluenesulfonic acid in toluene at reflux, the desired rearrangement took place in high yield. 

The formation of 2-arylamino-2-deoxyaldoses in the reaction of ketoses with anilines was described as the retro-Amadori reaction (called also the Heyns rearrangement)145. 

J. Z. Mioduszewski, K. Witkiewicz, and A. Inglot, Amadori reaction products, process for their manufacture, and their use in pharmaceuticals and cosmetics, Int. Pat. Appl, (1993) WO 9316087. 

U. Hommel, M. Eberhard, and K. Kirsehner, Phosphoribosyl anthranilate isomerase eafalyzes a reversible Amadori reaction. Biochemistry, 34 (1995) 5429-5439. 

A kinetic analysis of the Amadori reaction of glucose with morpholine has been reported, and a study that provides further evidence for the reversibility of the Amadori reaction is covered in Chapter 9 (Section 3.8). 

By Amadori Reaction. — 1-Amino-1-deoxy-D-fnictose derivatives (Amadori compounds) have been prepared by reaction of D-glucose vith a series of aliphatic amino acids (e.g. glycine, P-alanine, y-aminobutyric acid, 5-aminovaleric acid, e-aminocaproic acid and AT-formyl-L-lysine), and characterized by H- and C-n.m.r. and FAB-mass spectrometry and pH-potentiometric titration. The P-pyranose form dominates in aqueous solution. The basicity of the amino-group in these compounds is decreased (by -1.5 of the IKa value) relative to the parent amino acid. The formation of l-)V-butylamino-l-deoxy-4-0-(a-D-glucopyranosyl)-D-fructose by Amadori reaction of maltose and butylamine, and its conversion to the amino-reductone 23 have been reported. ... 

Amadori reaction. - The 1-amino-1-deoxy-D-fructose derivative 5 was synthesized by condensation of D-glucose with hippuryl-lysine in methanol it was intended for use as a standard in the analysis of protein-fhictosamines by reaction with nitro blue tetrazolinium (NBT) undo alkaline conditions, but it and related peptide-fructosamines gave much lower relative responses than the protein-fructosamines in this assay. ... 

The Heyns rearrangement suffers from the same shortcomings as the Amadori reaction (Sect. 2.6). One of the main problems is the competition between the rearrangement reaction and the hydrolysis of the initially formed ketosylamine, the latter leading back to the starting material. 

The synthesis and mutagenic effect upon Salmonella tvphimurium of l-deoxy-l-(p-tolylamino)-D-fructose, nine related glycosylamines, and their M-nitroso derivatives have been reported. It was suggested that mutagenicity was associated with production of the arenediazonium cation.The Amadori reaction between D-glucose and glycine led to the expected fructose-glycine condensation product which was shown to exist mainly in the... 

Chrysopine 1, the spiro-lactone of Ar -(l-deoxy-D-fructos-l-yl)-L-glutamine, and thus a product of the Amadori reaction of glucose with glutamine, has been isolated from crown gall tumours induced on tobacco plants by Agrobacterium twnefaciens. Its anomeric configuration was not determined. ... 

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