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 ...

, a stereocenter of a

molecule A molecule is a group of two or more atoms that are held together by Force, attractive forces known as chemical bonds; depending on context, the term may or may not include ions that satisfy this criterion. In quantum physics, organic chemi ...

is an

atom Atoms are the basic particles of the chemical elements. An atom consists of a atomic nucleus, nucleus of protons and generally neutrons, surrounded by an electromagnetically bound swarm of electrons. The chemical elements are distinguished fr ...

(center), axis or plane that is the focus of

stereoisomerism 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 ...

; 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. A stereocenter is geometrically defined as a point (location) in a molecule; a stereocenter is usually but not always a specific atom, often carbon. Stereocenters can exist on

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 ...

or achiral molecules; stereocenters can contain single bonds or double bonds. The number of hypothetical stereoisomers can be predicted by using 2^''n'', with ''n'' being the number of

tetrahedral In geometry, a tetrahedron (: tetrahedra or tetrahedrons), also known as a triangular pyramid, is a polyhedron composed of four triangular Face (geometry), faces, six straight Edge (geometry), edges, and four vertex (geometry), vertices. The tet ...

stereocenters; however, exceptions such as meso compounds can reduce the prediction to below the expected 2^''n''. Chirality centers are a type of stereocenter with four different substituent groups; chirality 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

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 having multiple stereocenters will produce many possible stereoisomers. In compounds whose stereoisomerism is due to

(sp³) stereogenic centers, the total number of hypothetically possible stereoisomers will not exceed 2^''n'', 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 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 ...

(non-superposable mirror images) and

diastereomers 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 dif ...

(non-superposable, non-identical, non-mirror image 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 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 ...

, which is an achiral compound that is superposable on its mirror image; the presence of a meso compound will reduce the number of possible stereoisomers. Since a meso compound is superposable on its mirror image, the two "stereoisomers" are actually identical. Resultantly, a meso compound will reduce the number of stereoisomers to below the hypothetical 2^''n'' 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.

Chirality centers

A chirality center (chiral center) is a type of stereocenter. A chirality center is defined as an atom holding a set of four different

ligands In coordination chemistry, a ligand is an ion or molecule with a functional group that binds to a central metal atom to form a coordination complex. The bonding with the metal generally involves formal donation of one or more of the ligand's ...

(atoms or groups of atoms) in a spatial arrangement which is non-superposable on its mirror image. Chirality centers must be sp³ hybridized, meaning that a chirality center can only have single bonds. In

organic chemistry Organic chemistry is a subdiscipline within chemistry involving the science, scientific study of the structure, properties, and reactions of organic compounds and organic matter, organic materials, i.e., matter in its various forms that contain ...

, a chirality center usually refers to a

carbon Carbon () is a chemical element; it has chemical symbol, symbol C and atomic number 6. It is nonmetallic and tetravalence, tetravalent—meaning that its atoms are able to form up to four covalent bonds due to its valence shell exhibiting 4 ...

phosphorus Phosphorus is a chemical element; it has Chemical symbol, symbol P and atomic number 15. All elemental forms of phosphorus are highly Reactivity (chemistry), reactive and are therefore never found in nature. They can nevertheless be prepared ar ...

, or

sulfur Sulfur ( American spelling and the preferred IUPAC name) or sulphur ( Commonwealth spelling) is a chemical element; it has symbol S and atomic number 16. It is abundant, multivalent and nonmetallic. Under normal conditions, sulfur atoms ...

atom, though it is also possible for other atoms to be chirality centers, especially in areas of

organometallic Organometallic chemistry is the study of organometallic compounds, chemical compounds containing at least one chemical bond between a carbon atom of an organic molecule and a metal, including alkali, alkaline earth, and transition metals, and so ...

and

inorganic chemistry Inorganic chemistry deals with chemical synthesis, synthesis and behavior of inorganic compound, inorganic and organometallic chemistry, organometallic compounds. This field covers chemical compounds that are not carbon-based, which are the subj ...

. The concept of a chirality center generalizes the concept of an asymmetric carbon atom (a carbon atom bonded to four different entities) to a broader definition of any atom with four different attachment groups in which an interchanging of any two attachment groups gives rise to an

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 ...

Stereogenic on carbon

A carbon atom that is attached to four different substituent groups is called an '' asymmetric carbon atom'' or ''chiral carbon''. Chiral carbons are the most common type of chirality center.

Stereogenic 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 In chemistry, amines (, ) are organic compounds that contain carbon-nitrogen bonds. Amines are formed when one or more hydrogen atoms in ammonia are replaced by alkyl or aryl groups. The nitrogen atom in an amine possesses a lone pair of elec ...

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

at that nitrogen are present under normal circumstances. Racemization by nitrogen inversion may be restricted (such as quaternary ammonium or

phosphonium In chemistry, the term phosphonium (more obscurely: phosphinium) describes polyatomic cations with the chemical formula (where R is a hydrogen or an alkyl, aryl, organyl or halogen group). These cations have tetrahedral structures. The ...

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.

Chirality and stereocenters

As mentioned earlier, the requirement for an atom to be a chirality center is that the atom must be sp³ hybridized with four different attachments. Because of this, all chirality 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 although all chirality centers are stereocenters, not every stereocenter is a chirality center. Stereocenters are important identifiers for chiral or achiral molecules. As a general rule, if a molecule has no stereocenters, it is considered 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 molecules with multiple stereocenters considered achiral.

References

{{Chiral synthesis Stereochemistry