stereochemistry Stereochemistry, a subdiscipline of chemistry, studies the spatial arrangement of atoms that form the structure of molecules and their manipulation. The study of stereochemistry focuses on the relationships between stereoisomers, which are defined ...

, diastereomers (sometimes called diastereoisomers) are a type of

stereoisomer In stereochemistry, stereoisomerism, or spatial isomerism, is a form of isomerism in which molecules have the same molecular formula and sequence of bonded atoms (constitution), but differ in the three-dimensional orientations of their atoms in ...

. 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)

stereocenter In stereochemistry, a stereocenter of a molecule is an atom (center), axis or plane that is the focus of stereoisomerism; that is, when having at least three different groups bound to the stereocenter, interchanging any two different groups cr ...

s and are not mirror images of each other. When two diastereoisomers differ from each other at only one stereocenter, they are

epimer In stereochemistry, an epimer is one of a pair of diastereomers. The two epimers have opposite configuration at only one stereogenic center out of at least two. All other stereogenic centers in the molecules are the same in each. Epimerization is t ...

s. Each stereocenter gives rise to two different configurations and thus typically increases the number of stereoisomers by a factor of two. Diastereomers differ from

enantiomer In chemistry, an enantiomer (Help:IPA/English, /ɪˈnænti.əmər, ɛ-, -oʊ-/ Help:Pronunciation respelling key, ''ih-NAN-tee-ə-mər''), also known as an optical isomer, antipode, or optical antipode, is one of a pair of molecular entities whi ...

s 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 In chemistry, reactivity is the impulse for which a chemical substance undergoes a chemical reaction, either by itself or with other materials, with an overall release of energy. ''Reactivity'' refers to: * the chemical reactions of a single sub ...

. Diastereomers differ not only in physical properties but also in chemical reactivity — how a compound reacts with others. Glucose and

galactose Galactose (, ''wikt:galacto-, galacto-'' + ''wikt:-ose#Suffix 2, -ose'', ), sometimes abbreviated Gal, is a monosaccharide sugar that is about as sweetness, sweet as glucose, and about 65% as sweet as sucrose. It is an aldohexose and a C-4 epime ...

, 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 Organic reactions are chemical reactions involving organic compounds. The basic organic chemistry reaction types are addition reactions, elimination reactions, substitution reactions, pericyclic reactions, rearrangement reactions, mechanistic organ ...

. In general,

stereoselectivity In chemistry, stereoselectivity is the property of a chemical reaction in which a single reactant forms an unequal mixture of stereoisomers during a non- stereospecific creation of a new stereocenter or during a non-stereospecific transformation ...

is attributed to torsional and steric interactions in the

resulting from

electrophile In chemistry, an electrophile is a chemical species that forms bonds with nucleophiles by accepting an electron pair. Because electrophiles accept electrons, they are Lewis acids. Most electrophiles are positively Electric charge, charged, have an ...

s approaching the stereocenter in reaction.

Syn / anti

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.

Erythro / threo

Two older prefixes still commonly used to distinguish diastereomers are threo and erythro. In the case of saccharides, when drawn in the

Fischer projection In chemistry, the Fischer projection, devised by Emil Fischer in 1891, is a two-dimensional representation of a three-dimensional organic molecule by projection. Fischer projections were originally proposed for the depiction of carbohydrates a ...

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

aldose An aldose is a monosaccharide (a simple sugar) with a carbon backbone chain with a carbonyl group on the endmost carbon atom, making it an aldehyde, and hydroxyl groups connected to all the other carbon atoms. Aldoses can be distinguished from ket ...

erythrose Erythrose is a tetrose saccharide with the chemical formula C4H8O4. It has one aldehyde group, and is thus part of the aldose family. The natural isomer is D-erythrose; it is a diastereomer of D -threose. Erythrose was first isolated in 1849 ...

and

threose Threose is a four-carbon monosaccharide with molecular formula C4H8O4. It has a terminal aldehyde group, rather than a ketone, in its linear chain and so is considered part of the aldose family of monosaccharides. The threose name can be used to ...

. These prefixes are not recommended for general use because it is often difficult to discern how to apply their definitions to particular comounds. However, the prefixes can usefully describe the

relative configuration Relative may refer to: General use *Kinship and family, the principle binding the most basic social units of society. If two people are connected by circumstances of birth, they are said to be ''relatives''. Philosophy *Relativism, the concept t ...

of a compound that has the following properties: it has at least four C atoms, exactly two of those C atoms are

stereocenters In stereochemistry, a stereocenter of a molecule is an atom (center), axis or plane that is the focus of stereoisomerism; that is, when having at least three different groups bound to the stereocenter, interchanging any two different groups cr ...

, the stereocenters are adjacent, and the two substituents on each stereocenter can clearly be labeled as "larger" (usually a

heteroatom In chemistry, a heteroatom () is, strictly, any atom that is not carbon or hydrogen. Organic chemistry In practice, the term is mainly used more specifically to indicate that non-carbon atoms have replaced carbon in the backbone of the molecular ...

such as N, O, or S) and "smaller" (usually H).

Threitol Threitol is the chiral four-carbon sugar alcohol with the molecular formula C4H10O4. It is primarily used as an intermediate in the chemical synthesis of other compounds. It exists in the enantiomorphic forms D-threitol and L-threitol, the reduc ...

and

erythritol Erythritol (, ) is an organic compound, the naturally occurring achiral meso four-carbon sugar alcohol (or polyol). It is the reduced form of either D- or L- erythrose and one of the two reduced forms of erythrulose. It is used as a food ad ...

are both four-carbon

sugar alcohols Sugar alcohols (also called polyhydric alcohols, polyalcohols, alditols or glycitols) are organic compounds, typically derived from sugars, containing one hydroxyl group attached to each carbon atom. They are white, water-soluble solids that ca ...

. Erythritol is

achiral Chirality () is a property of asymmetry important in several branches of science. The word ''chirality'' is derived from the Greek (''kheir''), "hand", a familiar chiral object. An object or a system is ''chiral'' if it is distinguishable from ...

(has at least one conformation with a plane or center of symmetry), whereas threitol is chiral. A useful English-language

mnemonic device A mnemonic device ( ), memory trick or memory device is any learning technique that aids information retention or retrieval in the human memory, often by associating the information with something that is easier to remember. It makes use of e ...

is that "threitol" and "chiral" both begin with consonants, whereas "erythritol" and "achiral" both begin with vowels. Another threo compound is

threonine Threonine (symbol Thr or T) is an amino acid that is used in the biosynthesis of proteins. It contains an α-amino group (which is in the protonated −NH form when dissolved in water), a carboxyl group (which is in the deprotonated −COO− ...

, one of the

amino acids Amino acids are organic compounds that contain both amino and carboxylic acid functional groups. Although over 500 amino acids exist in nature, by far the most important are the Proteinogenic amino acid, 22 α-amino acids incorporated into p ...

coded by

DNA Deoxyribonucleic acid (; DNA) is a polymer composed of two polynucleotide chains that coil around each other to form a double helix. The polymer carries genetic instructions for the development, functioning, growth and reproduction of al ...

. Its erythro diastereomer,

allothreonine Allothreonine is an amino acid with the formula . It is the diastereomer of the amino acid threonine. Like most other amino acids, allothreonine is a water-soluble colorless solid. Although not one of the proteinogenic amino acids, it has often ...

, is not coded by DNA and is very rare in nature. In

alkene In organic chemistry, an alkene, or olefin, is a hydrocarbon containing a carbon–carbon double bond. The double bond may be internal or at the terminal position. Terminal alkenes are also known as Alpha-olefin, α-olefins. The Internationa ...

addition reactions, syn addition to a trans alkene, or anti addition to a cis alkene, gives a threo product, whereas syn addition to a cis alkene, or anti addition to a trans alkene, gives an erythro product.

Multiple stereocenters

If a molecule contains two asymmetric centers, there are up to four possible configurations, and they cannot all be non-superposable mirror images of each other. The possibilities for different isomers continue to multiply as more stereocenters are added to a molecule. In general, the number of stereoisomers of a molecule can be determined by calculating 2^''n'', where ''n'' = the number of

chiral Chirality () is a property of asymmetry important in several branches of science. The word ''chirality'' is derived from the Greek language, Greek (''kheir''), "hand", a familiar chiral object. An object or a system is ''chiral'' if it is dist ...

centers in the molecule. This holds true except in cases where the molecule has meso forms. These

meso compound A meso compound or meso isomer is an optically inactive isomer in a set of stereoisomers, at least two of which are optically active. This means that despite containing two or more stereocenters, the molecule is not chiral. A meso compound is su ...

s are molecules that contain

s, but possess an internal plane of symmetry allowing it to be superposed on its mirror image. These equivalent configurations cannot be considered diastereomers. For ''n'' = 3, there are eight stereoisomers. Among them, there are four pairs of enantiomers: R,R,R and S,S,S; R,R,S and S,S,R; R,S,S and S,R,R; and R,S,R and S,R,S. There are many more pairs of diastereomers, because each of these configurations is a diastereomer with respect to every other configuration excluding its own enantiomer (for example, R,R,R is a diastereomer of R,R,S; R,S,R; and R,S,S). For ''n'' = 4, there are sixteen stereoisomers, or eight pairs of enantiomers. The four enantiomeric pairs of aldopentoses and the eight enantiomeric pairs of aldohexoses (subsets of the five- and six-carbon sugars) are examples of sets of compounds that differ in this way.

Diastereomerism at a double bond

Double bond isomers are always considered diastereomers, not enantiomers. Diastereomerism can also occur at a

double bond In chemistry, a double bond is a covalent bond between two atoms involving four bonding electrons as opposed to two in a single bond. Double bonds occur most commonly between two carbon atoms, for example in alkenes. Many double bonds exist betw ...

, where the ''cis'' vs ''trans'' relative positions of

substituents In organic chemistry, a substituent is one or a group of atoms that replaces (one or more) atoms, thereby becoming a moiety (chemistry), moiety in the resultant (new) molecule. The suffix ''-yl'' is used when naming organic compounds that conta ...

give two non-superposable isomers. Many conformational isomers are diastereomers as well. In the case of diastereomerism occurring at a double bond, E-Z, or entgegen and zusammen (German), is used in notating

nomenclature Nomenclature (, ) is a system of names or terms, or the rules for forming these terms in a particular field of arts or sciences. (The theoretical field studying nomenclature is sometimes referred to as ''onymology'' or ''taxonymy'' ). The principl ...

Applications

As stated previously, two diastereomers will not have identical chemical properties. This knowledge is harnessed in

chiral synthesis Enantioselective synthesis, also called asymmetric synthesis, is a form of chemical synthesis. It is defined by IUPAC as "a chemical reaction (or reaction sequence) in which one or more new elements of chirality are formed in a substrate molecul ...

to separate a mixture of enantiomers. This is the principle behind

chiral resolution Chiral resolution, or enantiomeric resolution, is a process in stereochemistry for the separation of racemic mixture into their enantiomers. It is an important tool in the production of optically active compounds, including drugs. Another term wit ...

. After preparing the diastereomers, they are separated by

chromatography In chemical analysis, chromatography is a laboratory technique for the Separation process, separation of a mixture into its components. The mixture is dissolved in a fluid solvent (gas or liquid) called the ''mobile phase'', which carries it ...

or recrystallization. Note also the example of the stereochemistry of ketonization of enols and enolates.

References