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Amadori Rearrangement: History
Please note this is an old version of this entry, which may differ significantly from the current revision.
Subjects: Chemistry, Organic
Contributor: Helena Kang

The Amadori rearrangement is the acid- or base-mediated conversion of an N-substituted glycosylamine derived from an aldose into the corresponding 1-amino-1-deoxy-2-ketose. Initial condensation of the aldose carbonyl group with a primary amine gives an imine that cyclizes and equilibrates with glycosylamine forms. Ring opening, proton transfer through an enaminol intermediate, and reorganization of the carbonyl system shift the carbonyl functionality from C1 to C2 while retaining the nitrogen substituent at C1 [1]. The resulting ketoamine is called an Amadori product. This transformation is distinguished from the Heyns rearrangement, in which a ketose-derived glycosylamine gives a 2-amino-2-deoxyaldose, and from later dehydration, fragmentation, or oxidation reactions of the ketoamine [2]. The conceptual endpoint is the rearranged aminodeoxyketose itself; subsequent formation of heterocycles, cross-links, or advanced glycation products lies outside the definition of the rearrangement.

  • Amadori rearrangement
  • glycosylamine
  • ketoamine
  • aminodeoxyketose

Advanced Glycation End Products research • Clinical Biochemistry • Biochemistry, Genetics and Molecular Biology • Life Sciences

References

  1. J. E. Hodge; Dehydrated Foods, Chemistry of Browning Reactions in Model Systems. J. Agric. Food Chem. 1953, 1, 928-943, 10.1021/jf60015a004.
  2. F. Micheel; Mechanism of Osazone Formation and of the Amadori Rearrangement. Angew. Chem. Int. Ed. Engl. 1964, 3, 320-320, 10.1002/anie.196403202.
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