Diastereomer

In stereochemistry, diastereomers (sometimes called diastereoisomers) are a type of stereoisomer. Diastereomers are defined as non-mirror image, non-identical stereoisomers. Hence, they occur when two or more stereoisomers of a compound have different configurations at one or more (but not all) of the equivalent (related) stereocenters and are not mirror images of each other. When two diastereoisomers differ from each other at only one stereocenter, they are epimers. Each stereocenter gives rise to two different configurations and thus typically increases the number of stereoisomers by a factor of two.

Diastereomers differ from enantiomers in that the latter are pairs of stereoisomers that differ in all stereocenters and are therefore mirror images of one another. Enantiomers of a compound with more than one stereocenter are also diastereomers of the other stereoisomers of that compound that are not their mirror image (that is, excluding the opposing enantiomer). Diastereomers have different physical properties (unlike most aspects of enantiomers) and often different chemical reactivity.

Diastereomers differ not only in physical properties but also in chemical reactivity — how a compound reacts with others. Glucose and galactose, for instance, are diastereomers. Even though they share the same molar weight, glucose is more stable than galactose. This difference in stability causes galactose to be absorbed slightly faster than glucose in the human body.

Diastereoselectivity is the preference for the formation of one or more than one diastereomer over the other in an organic reaction. In general, stereoselectivity is attributed to torsional and steric interactions in the stereocenter resulting from electrophiles approaching the stereocenter in reaction.

When the single bond between the two centres is free to rotate, cis/trans descriptors become invalid. Two widely accepted prefixes used to distinguish diastereomers on sp³-hybridised bonds in an open-chain molecule are syn and anti. Masamune proposed the descriptors which work even if the groups are not attached to adjacent carbon atoms. It also works regardless of CIP priorities. Syn describes groups on the same face while anti describes groups on opposite faces. The concept applies only to the Zigzag projection. The descriptors only describe relative stereochemistry rather than absolute stereochemistry. All isomers are same.

Two older prefixes still commonly used to distinguish diastereomers are threo and erythro. In the case of saccharides, when drawn in the Fischer projection the erythro isomer has two identical substituents on the same side and the threo isomer has them on opposite sides. When drawn as a zig-zag chain, the erythro isomer has two identical substituents on different sides of the plane (anti). The names are derived from the diastereomeric four-carbon aldoses erythrose and threose. These prefixes are not recommended for general use because it is often difficult to discern how to apply their definitions to particular compounds. However, the prefixes can usefully describe the relative configuration of a compound that has the following properties: it has at least four C atoms, exactly two of those C atoms are stereocenters, the stereocenters are adjacent, and the two substituents on each stereocenter can clearly be labeled as "larger" (usually a heteroatom such as N, O, or S) and "smaller" (usually H).

Threitol and erythritol are both four-carbon sugar alcohols. Erythritol is achiral (has at least one conformation with a plane or center of symmetry), whereas threitol is chiral. A useful English-language mnemonic device is that "threitol" and "chiral" both begin with consonants, whereas "erythritol" and "achiral" both begin with vowels.

Another threo compound is threonine, one of the amino acids coded by DNA. Its erythro diastereomer, allothreonine, is not coded by DNA and is very rare in nature.