User:ChemistryCat123/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 creates a new stereoisomer. Stereocenters are also referred to as stereogenic centers.

The term stereocenter was introduced in 1984 by Kurt Mislow and Jay Siegel. A stereocenter is geometrically defined as a point (location) in a molecule; a stereocenter is not necessarily a specific atom. Stereocenters can exist on chiral or achiral molecules; stereocenters can contain single bonds or double bonds. The number of hypothetical stereoisomers can be predicted by using 2n, with n being the number of tetrahedral stereocenters; however, exceptions such as meso compounds can reduce the prediction to below the expected 2n.

Chiral centers are a type of stereocenter with four different substituent groups; chiral centers are a specific subset of stereocenters because they can only have sp3 hybridization, meaning that they can only have single bonds.

Location
Stereocenters can exist on chiral or achiral molecules. They are defined as a location (point) within a molecule, rather than a particular atom, in which the interchanging of two groups creates a stereoisomer. A stereocenter can have either four different attachment groups, or three different attachment groups where one group is connected by a double bond. Since stereocenters can exist on achiral molecules, stereocenters can have either sp3 or sp2 hybridization.

Possible Number of Stereoisomers
Stereoisomers are compounds that are identical in composition and connectivity but have a different spatial arrangement of atoms around the central atom. A molecule can have multiple stereocenters, producing many possible stereoisomers. In compounds whose stereoisomerism is due to tetrahedral (sp3) stereogenic centers, the total number of hypothetically possible stereoisomers will not exceed 2n, where n is the number of tetrahedral stereocenters. However, this is an upper bound because molecules with symmetry frequently have fewer stereoisomers.

The stereoisomers produced by the presence of multiple stereocenters can be defined as enantiomers (non-superimposable mirror images) and diastereomers (non-superimposable, non-identical molecules). Enantiomers and diastereomers are produced due to differing stereochemical configurations of molecules containing the same composition and connectivity (bonding); the molecules must have multiple (two or more) stereocenters to be classified as enantiomers or diastereomers. Enantiomers and diastereomers will produce individual stereoisomers that contribute to the total number of possible stereoisomers.

However, the stereoisomers produced may also give a meso compound, which is an achiral compound that is superimposable on its mirror image; the presence of a meso compound will reduce the number of stereoisomers. Since the meso compound is superimposable on its mirror image, the two stereoisomers are actually identical. Resultantly, a meso compound will reduce the number of stereoisomers to below the hypothetical 2n amount due to symmetry.

Additionally, certain configurations may not exist due to steric reasons. Cyclic compounds with chiral centers may not exhibit chirality due to the presence of a two-fold rotation axis. Planar chirality may also provide for chirality without having an actual chiral center present.

Configuration
Configuration is defined as the arrangement of atoms around a stereocenter. The Cahn-Ingold-Prelog (CIP) system uses R and S designations to define the configuration of atoms about any stereocenter. A designation of R denotes a clockwise direction of substituent priority around the stereocenter, while a designation of S denotes a counter-clockwise direction of substituent priority.

Chiral Centers
A chiral center is a type of stereocenter. A chiral center is defined as a central atom holding a set of four different ligands (atoms or groups of atoms) in a spatial arrangement which is non-superimposable on its mirror image. Chiral centers must be sp3 hybridized, meaning that a chiral center can only have single bonds. In organic chemistry, a chiral center usually refers to a carbon, phosphorus, or sulfur atom, though it is possible for other atoms to be chiral centers, especially in areas of organometallic and inorganic chemistry.

The most common chiral center is a carbon atom. Chiral centers generalize the concept of an asymmetric carbon atom (a carbon atom bonded to four unique entities) such that an interchanging of any two groups gives rise to an enantiomer.

Chirality and Stereocenters
As mentioned earlier, the requirement for an atom to be a chiral center is that the atom must be sp3 hybridized with four different attachments. Because of this, all chiral centers are stereocenters. However, only under some conditions is the reverse true. Recall that a point can be considered a sterocenter with a minimum of three attachment points; stereocenters can be either sp3 or sp2 hybridized, as long as the interchanging any two different groups creates a new stereoisomer. This means that not every stereocenter is a chiral center.

Stereocenters are important identifiers for chiral or achiral molecules. As a general rule, if a molecule has no stereocenters, it is achiral. If it has at least one stereocenter, the molecule has the potential for chirality. However, there are some exceptions like meso compounds that make molecule with multiple stereocenters considered achiral.

Stereocenters on Other Atoms
Chirality is not limited to carbon atoms, though carbon atoms are often centers of chirality due to their ubiquity in organic chemistry. Nitrogen and phosphorus atoms can also form bonds in a tetrahedral configuration. A nitrogen in an amine may be a stereocenter if all three groups attached are different because the electron pair of the amine functions as a fourth group. However, nitrogen inversion, a form of pyramidal inversion, causes racemization which means that both epimers at that nitrogen are present under normal circumstances. Racemization by nitrogen inversion may be restricted (such as quaternary ammonium or phosphonium cations), or slow, which allows the existence of chirality.

Metal atoms with tetrahedral or octahedral geometries may also be chiral due to having different ligands. For the octahedral case, several chiralities are possible. Having three ligands of two types, the ligands may be lined up along the meridian, giving the mer-isomer, or forming a face—the fac isomer. Having three bidentate ligands of only one type gives a propeller-type structure, with two different enantiomers denoted Λ and Δ.