A glycosidic bond is formed between the hemiacetal group of a saccharide (or a molecule derived from a saccharide) and the hydroxyl group of some organic compound such as an alcohol. If the group attached to the carbohydrate residue is not another saccharide it is referred to as an aglycone. If it is another saccharide, the resulting units can be termed as being at the reducing end or the terminal end of the structure. This is a relative nomenclature where the reducing end of the di- or polysaccharide is towards the last anomeric carbon of the structure, and the terminal end is in the opposite direction.
In the literature, the bond between an amino group or other nitrogen-containing group and the sugar is often referred to as a glycosidic bond (although IUPAC seems to suggest that the term is a misnomer). For example, the sugar-base bond in a nucleoside may be referred to as a glycosidic bond. A substance containing a glycosidic bond is a glycoside.
S-, N-, C-, and O-glycosidic bonds
Glycosidic bonds of the form discussed above are known as O-glycosidic bonds, in reference to the glycosidic oxygen that links the glycoside to the aglycone or reducing end sugar. In analogy, one also considers S-glycosidic bonds (which form thioglycosides), where the oxygen of the glycosidic bond is replaced with a sulfur atom. In the same way, N-glycosidic bonds, have the glycosidic bond oxygen replaced with nitrogen. Substances containing N-glycosidic bonds are also known as glycosylamines; the term "N-glycoside" is considered a misnomer by IUPAC and is discouraged. C-glycosyl bonds have the glycosidic oxygen replaced by a carbon. All of these modified glycosidic bonds have different susceptibility to hydrolysis, and in the case of C-glycosyl structures, they are typically more resistant to hydrolysis.
Numbering, and α/β distinction of glycosidic bonds
One distinguishes between α- and β-glycosidic bonds based on the relative stereochemistry of the anomeric position and the stereocentre furthest from C1 in the saccharide. In D-hexose sugars in their pyranose forms, an α-glycosidic bond is formed in an axial orientation, whereas a β-glycosidic bond will be oriented equatorially.
Pharmacologists often join substances to glucuronic acid via glycosidic bonds in order to increase their water solubility; this is known as glucuronidation. Many other glycosides have important physiological functions.
Before monosaccharide units are incorporated into glycoproteins, polysaccharides, or lipids in living organisms, they are typically first "activated" by being joined via a glycosidic bond to the phosphate group of a nucleotide such as uridine diphosphate (UDP), guanosine diphosphate (GDP), thymidine diphosphate (TDP), or cytidine monophosphate (CMP). These activated biochemical intermediates are known as sugar nucleotides or sugar donors. Many biosynthetic pathways use mono- or oligosaccharides activated by a diphosphate linkage to lipids, such as dolichol. These activated donors are then substrates for enzymes known as glycosyltransferases, which transfer the sugar unit from the activated donor to an accepting nucleophile (the acceptor substrate).
- Andre A and Guschlbauer W. (1974). "Nucleoside conformations. 15. Flexibility of natural pyrimidine nucleosides around the glycosidic bond.". Nucleic Acids Res. 1 (6): 803–7. doi:10.1093/nar/1.6.803. PMC 343381. PMID 10793758.
- Definition of glycosides, from the IUPAC Compendium of Chemical Terminology, the "Gold Book"
- Varki A et al. Essentials of Glycobiology. Cold Spring Harbor Laboratory Press; 1999. Searchable online