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An anomer is a type of stereoisomer and epimer found in carbohydrate chemistry. While an epimer is a stereoisomer that differs in configuration at any single stereogenic center, an anomer is a cyclic saccharide and an epimer that differs in configuration, specifically at the hemiacetal/acetal carbon, also called the anomeric carbon.^[1] The anomeric carbon is the carbon derived from the carbonyl carbon (the ketone or aldehyde functional group) of the open-chain form of the carbohydrate molecule. Anomerization is the process of conversion of one anomer to the other.

Nomenclature

Different projections of α-D-glucopyranose. 1 = Fischer projection with C-1 at the top the anomeric centre. C-5 is the anomeric reference atom. 2,3 = Haworth projections. 4 = Mills projection.

Two anomers are designated alpha (α) or beta (β), according to the configurational relationship between the anomeric centre and the anomeric reference atom, hence they are relative stereodescriptors. ^[2] The anomeric centre in hemiacetals is the anomeric carbon C-1. In hemiketals it is the carbon derived from the carbonyl of the ketone (e.g. C-2 in D-fructose). In aldohexoses the anomeric reference atom is the stereocenter that is farthest from anomeric carbon in the ring (the configurational atom, defining the sugar as D or L). In α-D-glucopyranose the reference atom is C-5.

If in the cyclic Fischer projection^[3] the exocyclic oxygen atom at the anomeric centre is cis (on the same side) to the exocyclic oxygen attached to the anomeric reference atom (in the OH group) the anomer is α. If the two oxygens are trans (on different sides) the anomer is β.^[4]

Anomerization

Anomerization is the process of conversion of one anomer to the other. For reducing sugars, anomerization is referred to as mutarotation and occurs readily in solution and is catalyzed by acid and base. This reversible process typically leads to an anomeric mixture in which eventually an equilibrium is reached between the two single anomers. The ratio of the two anomers is specific for the regarding sugar. For example, regardless of the configuration of the starting D-glucose, a solution will gradually move towards being a mixture of approximately 64% β-D-glucopyranoside and 36% of α-D-glucopyranose. As the ratio changes, the optical rotation of the mixture changes; this phenomenon is called mutarotation.

Mechanism of anomerization

Open-chain form as an intermediate product between α and β anomer

Open-chain form of

D-galactose

Though the cyclic forms of sugars are usually heavily favoured, hemiacetals in aqueous solution are in equilibrium with their open-chain forms. In aldohexoses this equilibrium is established as the hemiacetal bond between C-1 (the carbon bound to two oxygens) and C-5 oxygen is cleaved (forming the open-chain compound) and reformed (forming the cyclic compound). When the hemiacetal group is reformed, the OH group on C-5 may attack either of the two stereochemically distinct sides of the aldehyde group on C-1. Which side it attacks on determines whether the α or β anomer is formed.

Anomerization of glycosides typically occurs under acidic conditions. Typically, anomerization occurs through protonation of the exocyclic acetal oxygen, ionization to form an oxocarbenium ion with release of an alcohol, and nucleophilic attack by an alcohol on the reverse face of the oxocarbenium ion, followed by deprotonation.

Physical properties and stability

Anomers are different in structure, and thus have different stabilizing and destabilizing effects from each other. The major contributors to the stability of a certain anomer are:

The anomeric effect, which stabilizes the anomer that has an electron withdrawing group (typically an oxygen or nitrogen atom) in axial orientation on the ring. This effect is abolished in polar solvents such as water.
1,3-diaxial interactions, which usually destabilize the anomer that has the anomeric group in an axial orientation on the ring. This effect is especially noticeable in pyranoses and other six-membered ring compounds. This is a major factor in water.
Hydrogen bonds between the anomeric group and other groups on the ring, leading to stabilization of the anomer.
Dipolar repulsion between the anomeric group and other groups on the ring, leading to destabilization of the anomer.

For D-glucopyranoside, the β-anomer is the more stable anomer in water. For D-mannopyranose, the α-anomer is the more stable anomer.

Because anomers are diastereomers of each other, they often differ in physical and chemical properties. One of the most important physical properties that is used to study anomers is the specific rotation, which can be monitored by polarimetry.

References

^ Francis Carey (2000). Organic Chemistry, McGraw-Hill Higher Education press (4th ed.).
^ IUPAC Gold Book α (alpha), β (beta)
^ http://www.chem.qmul.ac.uk/iupac/2carb/05.html
^ Nomenclature of Carbohydrates (Recommendations 1996) PDF

External links

http://www.cem.msu.edu/~reusch/VirtualText/carbhyd.htm
http://themedicalbiochemistrypage.org/carbohydrates.html

English Journal

Synthesis of some 2-alkoxy glyco-[2,1-d]-2-oxazolines and evaluation of their glycosylation reactivity.

Pertel SS, Kononov LO, Zinin AI, Chirva VJ, Kakayan ES.SourceDepartment of Organic and Biological Chemistry, V.I. Vernadsky Taurida National University, Vernadsky ave. 4, 95007 Simferopol, Crimea, Ukraine. orgchem@crimea.edu
Carbohydrate research.Carbohydr Res.2012 Jul 15;356:172-9. Epub 2012 Apr 2.
The synthesis of the title compounds using intramolecular nucleophilic substitution reactions in the molecules of the corresponding 2-alkoxycarbonylamino-2-deoxy glucosyl halides was studied. It was found that in contrast to the 2-alkyl (aryl) glyco-[2,1-d]-2-oxazolines, the synthesis of the target
PMID 22521206

Glycosidation of thioglycosides in the presence of bromine: mechanism, reactivity, and stereoselectivity.

Kaeothip S, Yasomanee JP, Demchenko AV.SourceDepartment of Chemistry and Biochemistry, University of Missouri-St. Louis, One University Boulevard, St. Louis, Missouri 63121, United States.
The Journal of organic chemistry.J Org Chem.2012 Jan 6;77(1):291-9. Epub 2011 Dec 21.
Elaborating on previous studies by Lemieux for highly reactive "armed" bromides, we discovered that β-bromide of the superdisarmed (2-O-benzyl-3,4,6-tri-O-benzoyl) series can be directly obtained from the thioglycoside precursor. When this bromide is glycosidated, α-glycosides form exclusively; ho
PMID 22136383

Japanese Journal

2,3-transカーバメート基を持つ糖構造の特異な反応性 : 糖化学におけるエンド開裂反応の再発見

有機合成化学協会誌 71(6), 616-624, 2013-06-01
NAID 10031178159

2,3-<i>trans</i>カーバメート基を持つ糖構造の特異な反応性：糖化学におけるエンド開裂反応の再発見

有機合成化学協会誌 71(6), 616-624, 2013
NAID 130003373306

Analysis of behavior of sodiated sugar hemiacetals under low-energy collision-induced dissociation conditions and application to investigating mutarotation and mechanism of a glycosidase