Amadori/Heyns

As illustrated in O Scheme 65, 33 reacts with an amine to give an imine 326 that isomerizes into an aminoketose 327 (Amadori product), existing as an equilibrium mixture of cyclic hemi-acetals, whereas 40 affords, by way of 328, the hexosamine derivatives 329 and 330 (Heyns products), also in cyclic form The Amadori-He)ms compounds index Amadori-Heyns com-pounds % are at the head of the complex sequences of the Maillard reaction. The crystal structure of the Amadori product 331 between 33 and glycine has been determined more than three decades after the first proposal of its structure. Alternative preparations and X-ray analyses of Heyns products 332 and 333 have been reported [273,274]. 

As indicated previously, primary and secondary amines can also react with carbonyl compounds to form a mixture of compounds containing small molecules and polymers. The small molecule compounds obtained from an aldose and an amine have the common name Amadori products because the Amadori rearrangement is involved in their formation. The compounds generated from ketoses and amines are known as Heyns products (although the differentiation Amadori/Heyns is not always considered). The mechanism for the reaction of primary amines with a reducing sugar can be formulated as follows ... 

A. Jakas, A. Katie, N. Bionda, and S. Horvat, Glycation of a lysine-containing tetrapeptide by D-glucose and D-fiuctose— influence of different reaction conditions on the formation of Amadori/Heyns products, Carbohydr. Res., 343 (2008) 2475-2480. 

An enantioselective Amadori-Heynes rearrangement of racemic a-hydrojgt ketones with arylamines to a-amino ketones with up to 81% ee catalysed by p-isocupreidine was also reported. ... 

Amadori/Heyns rearrangement -amino group Deoxyosones-----------------------------... 

Eder B, see Wrodnigg TM (2001) The Amadori and Heyns Rearrangements Landmarks in the History of Carbohydrate Chemistry or Unrecognized Synthetic Opportunities 215 115-175 Edwards DS, see Liu S (2002) 222 259-278... 

Mechanistische Untersuchungen fiber Glykosylamine, Zuckerhydrazone und Osazone d) Umlagerung nach Amadori bzw. Heyns... 

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