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 space. [1] [2] This contrasts with structural isomers, which share the same molecular formula, but the bond connections or their order differs. By definition, molecules that are stereoisomers of each other represent the same structural isomer. [3]
Enantiomers, also known as optical isomers, are two stereoisomers that are related to each other by a reflection: they are mirror images of each other that are non-superposable. Human hands are a macroscopic analog of this. Every stereogenic center in one has the opposite configuration in the other. Two compounds that are enantiomers of each other have the same physical properties, except for the direction in which they rotate polarized light and how they interact with different enantiomers of other compounds. As a result, different enantiomers of a compound may have substantially different biological effects. Pure enantiomers also exhibit the phenomenon of optical activity and can be separated only with the use of a chiral agent. In nature, only one enantiomer of most chiral biological compounds, such as amino acids (except glycine, which is achiral), is present. An optically active compound shows two forms: D-(+) form and L-(−) form.
Diastereomers are stereoisomers not related through a reflection operation. [4] They are not mirror images of each other. These include meso compounds, cis–trans isomers, E-Z isomers, and non-enantiomeric optical isomers. Diastereomers seldom have the same physical properties. In the example shown below, the meso form of tartaric acid forms a diastereomeric pair with both levo- and dextro-tartaric acids, which form an enantiomeric pair.
|  |  |
(natural) tartaric acid | D-tartaric acid | meso-tartaric acid |
(1:1) | ||
The D- and L- labeling of the isomers above is not the same as the d- and l- labeling more commonly seen, explaining why these may appear reversed to those familiar with only the latter naming convention.
A Fischer projection can be used to differentiate between L- and D- molecules Chirality (chemistry). For instance, by definition, in a Fischer projection the penultimate carbon of D-sugars are depicted with hydrogen on the left and hydroxyl on the right. L-sugars will be shown with the hydrogen on the right and the hydroxyl on the left.
The other refers to Optical rotation, when looking at the source of light, the rotation of the plane of polarization may be either to the right (dextrorotary — d-rotary, represented by (+), clockwise), or to the left (levorotary — l-rotary, represented by (−), counter-clockwise) depending on which stereoisomer is dominant. For instance, sucrose and camphor are d-rotary whereas cholesterol is l-rotary.
Stereoisomerism about double bonds arises because rotation about the double bond is restricted, keeping the substituents fixed relative to each other. [5] If the two substituents on at least one end of a double bond are the same, then there is no stereoisomer and the double bond is not a stereocenter, e.g. propene, CH3CH=CH2 where the two substituents at one end are both H. [6]
Traditionally, double bond stereochemistry was described as either cis (Latin, on this side) or trans (Latin, across), in reference to the relative position of substituents on either side of a double bond. A simple example of cis–trans isomerism is the 1,2-disubstituted ethenes, like the dichloroethene (C2H2Cl2) isomers shown below. [7]
Molecule I is cis-1,2-dichloroethene and molecule II is trans-1,2-dichloroethene. Due to occasional ambiguity, IUPAC adopted a more rigorous system wherein the substituents at each end of the double bond are assigned priority based on their atomic number. If the high-priority substituents are on the same side of the bond, it is assigned Z (Ger. zusammen, together). If they are on opposite sides, it is E (Ger. entgegen, opposite). [8] Since chlorine has a larger atomic number than hydrogen, it is the highest-priority group. [9] Using this notation to name the above pictured molecules, molecule I is (Z)-1,2-dichloroethene and molecule II is (E)-1,2-dichloroethene. It is not the case that Z and cis, or E and trans, are always interchangeable. Consider the following fluoromethylpentene:
The proper name for this molecule is either trans-2-fluoro-3-methylpent-2-ene because the alkyl groups that form the backbone chain (i.e., methyl and ethyl) reside across the double bond from each other, or (Z)-2-fluoro-3-methylpent-2-ene because the highest-priority groups on each side of the double bond are on the same side of the double bond. Fluoro is the highest-priority group on the left side of the double bond, and ethyl is the highest-priority group on the right side of the molecule.
The terms cis and trans are also used to describe the relative position of two substituents on a ring; cis if on the same side, otherwise trans. [10] [11]
Conformational isomerism is a form of isomerism that describes the phenomenon of molecules with the same structural formula but with different shapes due to rotations about one or more bonds. [12] [13] Different conformations can have different energies, can usually interconvert, and are very rarely isolatable. For example, there exists a variety of Cyclohexane conformations (which cyclohexane is an essential intermediate for the synthesis of nylon–6,6) including a chair conformation where four of the carbon atoms form the "seat" of the chair, one carbon atom is the "back" of the chair, and one carbon atom is the "foot rest"; and a boat conformation, the boat conformation represents the energy maximum on a conformational itinerary between the two equivalent chair forms; however, it does not represent the transition state for this process, because there are lower-energy pathways. The conformational inversion of substituted cyclohexanes is a very rapid process at room temperature, with a half-life of 0.00001 seconds. [14]
There are some molecules that can be isolated in several conformations, due to the large energy barriers between different conformations. 2,2',6,6'-Tetrasubstituted biphenyls can fit into this latter category.
Anomerism is an identity for single bonded ring structures where "cis" or "Z" and "trans" or "E" (geometric isomerism) needs to name the substitutions on a carbon atom that also displays the identity of chirality; so anomers have carbon atoms that have geometric isomerism and optical isomerism (enantiomerism) on one or more of the carbons of the ring. [15] [16] Anomers are named "alpha" or "axial" and "beta" or "equatorial" when substituting a cyclic ring structure that has single bonds between the carbon atoms of the ring for example, a hydroxyl group, a methyl hydroxyl group, a methoxy group or another pyranose or furanose group which are typical single bond substitutions but not limited to these. [17] Axial geometric isomerism will be perpendicular (90 degrees) to a reference plane and equatorial will be 120 degrees away from the axial bond or deviate 30 degrees from the reference plane. [18]
Atropisomers are stereoisomers resulting from hindered rotation about single bonds where the steric strain barrier to rotation is high enough to allow for the isolation of the conformers. [19]
Le Bel-van't Hoff rule states that for a structure with n asymmetric carbon atoms, there is a maximum of 2n different stereoisomers possible. As an example, D-glucose is an aldohexose and has the formula C6H12O6. Four of its six carbon atoms are stereogenic, which means D-glucose is one of 24=16 possible stereoisomers. [20] [21]
In organic chemistry, the Cahn–Ingold–Prelog (CIP) sequence rules are a standard process to completely and unequivocally name a stereoisomer of a molecule. The purpose of the CIP system is to assign an R or S descriptor to each stereocenter and an E or Z descriptor to each double bond so that the configuration of the entire molecule can be specified uniquely by including the descriptors in its systematic name. A molecule may contain any number of stereocenters and any number of double bonds, and each usually gives rise to two possible isomers. A molecule with an integer n describing the number of stereocenters will usually have 2n stereoisomers, and 2n−1 diastereomers each having an associated pair of enantiomers. The CIP sequence rules contribute to the precise naming of every stereoisomer of every organic molecule with all atoms of ligancy of fewer than 4.
Cis–trans isomerism, also known as geometric isomerism, describes certain arrangements of atoms within molecules. The prefixes "cis" and "trans" are from Latin: "this side of" and "the other side of", respectively. In the context of chemistry, cis indicates that the functional groups (substituents) are on the same side of some plane, while trans conveys that they are on opposing (transverse) sides. Cis–trans isomers are stereoisomers, that is, pairs of molecules which have the same formula but whose functional groups are in different orientations in three-dimensional space. Cis and trans isomers occur both in organic molecules and in inorganic coordination complexes. Cis and trans descriptors are not used for cases of conformational isomerism where the two geometric forms easily interconvert, such as most open-chain single-bonded structures; instead, the terms "syn" and "anti" are used.
In chemistry, a structural isomer of a compound is another compound whose molecule has the same number of atoms of each element, but with logically distinct bonds between them. The term metamer was formerly used for the same concept.
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 as having the same molecular formula and sequence of bonded atoms (constitution) but differing in the geometric positioning of the atoms in space. For this reason, it is also known as 3D chemistry—the prefix "stereo-" means "three-dimensionality". Stereochemistry applies to all kinds of compounds and ions, organic and inorganic species alike. Stereochemistry affects biological, physical, and supramolecular chemistry.
In chemistry, an enantiomer – also called optical isomer, antipode, or optical antipode – is one of a pair of molecular entities which are mirror images of each other and non-superposable. Enantiomers of each other are much like one's right and left hands; without mirroring one of them, hands cannot be superposed onto each other. It is solely a relationship of chirality and the permanent three-dimensional relationships among molecules or other chemical structures: no amount of re-orientiation of a molecule as a whole or conformational change converts one chemical into its enantiomer. Chemical structures with chirality rotate plane-polarized light. A mixture of equal amounts of each enantiomer, a racemic mixture or a racemate, does not rotate light.
The structural formula of a chemical compound is a graphic representation of the molecular structure, showing how the atoms are possibly arranged in the real three-dimensional space. The chemical bonding within the molecule is also shown, either explicitly or implicitly. Unlike other chemical formula types, which have a limited number of symbols and are capable of only limited descriptive power, structural formulas provide a more complete geometric representation of the molecular structure. For example, many chemical compounds exist in different isomeric forms, which have different enantiomeric structures but the same molecular formula. There are multiple types of ways to draw these structural formulas such as: Lewis structures, condensed formulas, skeletal formulas, Newman projections, Cyclohexane conformations, Haworth projections, and Fischer projections.
In chemistry, racemization is a conversion, by heat or by chemical reaction, of an optically active compound into a racemic form. This creates a 1:1 molar ratio of enantiomers and is referred to as a racemic mixture. Plus and minus forms are called Dextrorotation and levorotation. The D and L enantiomers are present in equal quantities, the resulting sample is described as a racemic mixture or a racemate. Racemization can proceed through a number of different mechanisms, and it has particular significance in pharmacology as different enantiomers may have different pharmaceutical effects.
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 creates a new stereoisomer. Stereocenters are also referred to as stereogenic centers.
In stereochemistry, diastereomers 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 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.
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 superposable on its mirror image. Two objects can be superposed if all aspects of the objects coincide and it does not produce a "(+)" or "(-)" reading when analyzed with a polarimeter. The name is derived from the Greek mésos meaning “middle”.
The skeletal formula, line-angle formula, bond-line formula or shorthand formula of an organic compound is a type of molecular structural formula that serves as a shorthand representation of a molecule's bonding and some details of its molecular geometry. A skeletal formula shows the skeletal structure or skeleton of a molecule, which is composed of the skeletal atoms that make up the molecule. It is represented in two dimensions, as on a piece of paper. It employs certain conventions to represent carbon and hydrogen atoms, which are the most common in organic chemistry.
In organic chemistry, butyl is a four-carbon alkyl radical or substituent group with general chemical formula −C4H9, derived from either of the two isomers (n-butane and isobutane) of butane.
In chemistry, a molecule or ion is called chiral if it cannot be superposed on its mirror image by any combination of rotations, translations, and some conformational changes. This geometric property is called chirality. The terms are derived from Ancient Greek χείρ (cheir) 'hand'; which is the canonical example of an object with this property.
The molecular configuration of a molecule is the permanent geometry that results from the spatial arrangement of its bonds. The ability of the same set of atoms to form two or more molecules with different configurations is stereoisomerism. This is distinct from constitutional isomerism which arises from atoms being connected in a different order. Conformers which arise from single bond rotations, if not isolatable as atropisomers, do not count as distinct molecular configurations as the spatial connectivity of bonds is identical.
In organic chemistry, the anomeric effect or Edward-Lemieux effect is a stereoelectronic effect that describes the tendency of heteroatomic substituents adjacent to a heteroatom within a cyclohexane ring to prefer the axial orientation instead of the less-hindered equatorial orientation that would be expected from steric considerations. This effect was originally observed in pyranose rings by J. T. Edward in 1955 when studying carbohydrate chemistry.
A cyclic compound is a term for a compound in the field of chemistry in which one or more series of atoms in the compound is connected to form a ring. Rings may vary in size from three to many atoms, and include examples where all the atoms are carbon, none of the atoms are carbon, or where both carbon and non-carbon atoms are present. Depending on the ring size, the bond order of the individual links between ring atoms, and their arrangements within the rings, carbocyclic and heterocyclic compounds may be aromatic or non-aromatic; in the latter case, they may vary from being fully saturated to having varying numbers of multiple bonds between the ring atoms. Because of the tremendous diversity allowed, in combination, by the valences of common atoms and their ability to form rings, the number of possible cyclic structures, even of small size numbers in the many billions.
In chemistry, absolute configuration refers to the spatial arrangement of atoms within a molecular entity that is chiral, and its resultant stereochemical description. Absolute configuration is typically relevant in organic molecules where carbon is bonded to four different substituents. This type of construction creates two possible enantiomers. Absolute configuration uses a set of rules to describe the relative positions of each bond around the chiral center atom. The most common labeling method uses the descriptors R or S and is based on the Cahn–Ingold–Prelog priority rules. R and S refer to rectus and sinister, Latin for right and left, respectively.
E–Z configuration, or the E–Z convention, is the IUPAC preferred method of describing the absolute stereochemistry of double bonds in organic chemistry. It is an extension of cis–trans isomer notation that can be used to describe double bonds having two, three or four substituents. E and Z notation are only used when a compound doesn't have two identical substituents.
In chemistry, isomers are molecules or polyatomic ions with identical molecular formula – that is, the same number of atoms of each element – but distinct arrangements of atoms in space. Isomerism refers to the existence or possibility of isomers.
In chemical nomenclature, a descriptor is a notational prefix placed before the systematic substance name, which describes the configuration or the stereochemistry of the molecule. Some of the listed descriptors should not be used in publications, as they no longer accurately correspond with the recommendations of the IUPAC. Stereodescriptors are often used in combination with locants to clearly identify a chemical structure unambiguously.
| Authority control databases: National |
|---|
