:Amadori rearrangement
{{Short description|Chemical reaction}}
The Amadori rearrangement is an organic reaction describing the acid or base catalyzed isomerization or rearrangement reaction of the N-glycoside of an aldose or the glycosylamine to the corresponding 1-amino-1-deoxy-ketose.Strategic Applications of Named Reactions in Organic Synthesis (Paperback) by Laszlo Kurti, BN 0-12-429785-4 The reaction is important in carbohydrate chemistry, specifically the glycation of hemoglobin (as measured by the HbA1c test).{{cite journal|title=Hemoglobin A Ic and diabetes mellitus|author1=Koenig, R. J. |author2=Cerami, A. |journal=Annual Review of Medicine|year=1980|volume=31|pages=29–34|doi=10.1146/annurev.me.31.020180.000333|pmid=6994614 }}
The rearrangement is usually preceded by formation of a α-hydroxyimine by condensation of an amine with an aldose sugar. The rearrangement itself entails intramolecular redox reaction, converting this α-hydroxyimine to an α-ketoamine:
The formation of imines is generally reversible, but subsequent to conversion to the keto-amine, the attached amine is fixed irreversibly. This Amadori product is an intermediate in the production of advanced glycation end-products (AGE)s. The formation of an advanced glycation end-product involves the oxidation of the Amadori product.
Food chemistry
The reaction is associated with the amino-carbonyl reactions (also called glycation reaction, or Maillard reaction){{cite web |last1=This vo Kientza |first1=Hervé |title=IMARS Highligh |url=https://www.imarsonline.com/ |website=www.imarsonline.com/}} in which the reagents are naturally occurring sugars and amino acids. One study demonstrated the possibility of Amadori rearrangement during interaction between oxidized dextran and gelatine.{{Cite journal |author1=Berillo, Dmitriy |author2=Natalia Volkova | title = Preparation and physicochemical characteristics of cryogel based on gelatin and oxidised dextran | journal = Journal of Materials Science | volume = 49 | issue = 14 | date = 2014 | pages = 4855–4868| bibcode = 2014JMatS..49.4855B | doi = 10.1007/s10853-014-8186-3 |s2cid=96843083 }}
History
The Amadori rearrangement was discovered by the organic chemist Mario Amadori (1886–1941), who in 1925 reported this reaction while studying the Maillard reaction.M. Amadori, Atti. reale accad. nazl. Lincei, [6] 2, 337 (1925); [6] 9, 68, 226 (1929); [6] 13, 72 (1931)Strategic Applications of Named Reactions in Organic Synthesis (Paperback) by Laszlo Kurti, BN 0-12-429785-4
See also
- Fructoselysine, the Amadori product derived from glucose and lysine
- Glycated hemoglobin, the Amadori product used in the HbA1c diagnostic test for diabetes
References
{{reflist}}
External links
- [https://web.archive.org/web/20061028061710/http://www.cfs.purdue.edu/class/f%26n630/amadori_rearrangement.ppt Amadori Rearrangement], PowerPoint presentation detailing the reaction mechanism
{{Organic reactions}}
Category:Rearrangement reactions