アマドリ転位、Amadori転位

WordNet

changing an arrangement

PrepTutorEJDIC

再整理,再配列

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出典(authority):フリー百科事典『ウィキペディア（Wikipedia）』「2014/03/29 19:45:03」(JST)

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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.^[1]^[2] The reaction is important in carbohydrate chemistry.

The reaction mechanism is demonstrated starting from the reaction of D-mannose in its closed (1) and open-form (2) with ammonia to produce the 1,1-amino-alcohol (3), which is unstable and loses water to the glycosylamine (again the open imine (5) and the closed form hemiaminal (4)), which is the starting point for the actual Amadori rearrangement.^[3]

By treatment of the glycosylamine with pyridine and acetic anhydride, the imine group rearranges and the intermediate enol, in turn, rearranges to the ketone. In this particular reaction, all the alcohol and amino groups are acylated as well.

The reaction is associated with the Maillard reaction in which the reagents are naturally occurring sugars and amino acids.

Amadori product[edit]

An Amadori product is an intermediate in the production of an advanced glycation end-product (AGE) as a result of glycation.

The formation of an advanced glycation end-product involves the following steps:

Formation of a Schiff base: For example the aldehyde group of a glucose molecule will combine with the amino group of a lysine molecule (in a protein) to form an imine or Schiff base, which is a double bond between the carbon atom of the glucose and the nitrogen atom of the lysine.
Formation of an Amadori product: The Amadori product is a re-arrangement from the Schiff base, wherein the hydrogen atom from the hydroxyl group adjacent to the carbon-nitrogen double bond moves to bond to the nitrogen, leaving a ketone.
Formation of an advanced glycation end-product (AGE): The Amadori product is oxidized, most often by transition metal catalysis.

The first two steps in this reaction are both reversible, but the last step is irreversible.

External links[edit]

Play by play Amadori rearrangement and more

References[edit]

^ 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
^ Mutarotation, Hydrolysis, and Rearrangement Reactions of Glycosylamines HORACE S. ISBELL and HARRIET L. FRUSH J. Org. Chem. 1958, 23(9), 1309 - 1319. (doi:10.1021/jo01103a019)

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English Journal

ZnCl2-mediated practical protocol for the synthesis of Amadori ketoses.

Harohally NV1, Srinivas SM2, Umesh S2.
Food chemistry.Food Chem.2014 Sep 1;158:340-4. doi: 10.1016/j.foodchem.2014.02.094. Epub 2014 Mar 5.
An efficient and practical protocol for the synthesis of Amadori ketoses N-(1-deoxy-D-fructose-1-yl) amino acid (amino acid=L-valine (1), L-leucine (2), L-isoleucine (3), L-tryptophan (4), L-phenylalanine (5), L-arginine (6) has been accomplished by employing ZnCl2 as a catalyst. The developed metho
PMID 24731352

The Maillard reaction of bisoprolol fumarate with various reducing carbohydrates.

Szalka M1, Lubczak J2, Naróg D3, Laskowski M4, Kaczmarski K5.
European journal of pharmaceutical sciences : official journal of the European Federation for Pharmaceutical Sciences.Eur J Pharm Sci.2014 Aug 1;59:1-11. doi: 10.1016/j.ejps.2014.04.005. Epub 2014 Apr 16.
HPLC analysis of drug products containing bisoprolol fumarate and lactose revealed the presence of N-formylbisoprolol, which is a final product of the Maillard reaction. Formulations containing secondary amines and reducing carbohydrates are prone to the condensation of amine and carbonyl functional
PMID 24746680

Characterization of the deoxyguanosine-lysine cross-link of methylglyoxal.

Petrova KV1, Millsap AD, Stec DF, Rizzo CJ.
Chemical research in toxicology.Chem Res Toxicol.2014 Jun 16;27(6):1019-29. doi: 10.1021/tx500068v. Epub 2014 May 15.
Methylglyoxal is a mutagenic bis-electrophile that is produced endogenously from carbohydrate precursors. Methylglyoxal has been reported to induce DNA-protein cross-links (DPCs) in vitro and in cultured cells. Previous work suggests that these cross-links are formed between guanine and either lysin
PMID 24801980

Japanese Journal

特異な複素環構造を有するバシロサルシンA, Bおよび関連化合物の合成研究

榎本賢,桑原重文
有機合成化学協会誌 68(4), 387-398, 2010-04-01
… The irregular ring systems in bacilosarcins A and B were constructed in very simple manners by means of an Amadori–type <I>N</I>–alkylation reaction as well as by taking advantage of the thermodynamic stability of the targeted rings. …
NAID 10026868671

Significance of Advanced Glycation End Products in Aging-Related Disease

Nagai Ryoji,Mori Takefumi,Yamamoto Yasuhiko,Kaji Yuichi,Yonei Yoshikazu
ANTI-AGING MEDICINE 7(10), 112-119, 2010
… This reaction is divided into early and advanced phase reactions: the former covers the reaction progression up to the Amadori rearrangement, and the latter covers the reaction through the subsequent alterations of oxidation, dehydration, condensation, and so on, eventually generating advanced glycation end products (AGEs). …
NAID 130000428490

Recent Advances in the Chemistry of Strecker Degradation and Amadori Rearrangement : Implications to Aroma and Color Formation

YAYLAYAN Varoujan A.
Food science and technology research 9(1), 1-6, 2003-02-01
… Strecker aldehyde can be formed directly either from free amino acids or from Amadori products. … On the other hand, Amadori or Heyns rearrangements of ammonia with reducing sugars can also generate 2-aminocarbonyl compounds without the formation of Strecker aldehyde. … The reverse of this reaction, has been documented to produce Amadori products. …
NAID 10011999832