This article needs attention from an expert in Chemistry. Please add a reason or a talk parameter to this template to explain the issue with the article. WikiProject Chemistry may be able to help recruit an expert. (February 2016)
Two enantiomers of a generic amino acid that is chiral
(S)-Alanine (left) and (R)-alanine (right) in zwitterionic form at neutral pH

Chirality/ˈkaɪərəl/ is a geometric property of some molecules and ions. A chiral molecule/ion is non-superposable on its mirror image. The presence of an asymmetric carbon atom is one of several structural features that induce chirality in organic and inorganic molecules.[1][page needed] [2][page needed] [3][4] The term chirality is derived from the Greek word for hand, χειρ (kheir).

The mirror images of a chiral molecule/ion are called enantiomers or optical isomers. Individual enantiomers are often designated as either "right-" or "left-handed". Chirality is an essential consideration when discussing the stereochemistry in inorganic chemistry and organic chemistry. The concept is of great practical importance because most biomolecules and pharmaceuticals are chiral. Chiral molecules and ions are described by various ways of designating absolute configuration. The absolute configuration codifies either the entity's geometry or its ability to rotate plane-polarized light, a common technique in the study of chirality.

History

The rotation of plane polarized light by chiral substances was first observed by Jean-Baptiste Biot in 1815,[5] and gained considerable importance in the sugar industry, analytical chemistry, and pharmaceuticals. Louis Pasteur deduced in 1848 that this phenomenon has a molecular basis.[6][7] The term chirality itself was coined by Lord Kelvin in 1894.[8][better source needed] Different enantiomers or diastereomers of a compound were formerly called optical isomers due to their different optical properties.[9] At one time, chirality was thought to be associated with organic chemistry, but this misconception was overthrown by the resolution of a purely inorganic compound, hexol, by Alfred Werner.

Symmetry

Symmetry elements of Formaldehyde

Chirality is based on molecular symmetry elements. Specifically, a chiral compound can contain no improper axis of rotation (Sn), which includes planes of symmetry and inversion center. Chiral molecules are always dysymmetric (lacking Sn) but not always asymmetric (lacking all symmetry elements except the trivial identity). Asymmetric molecules are always chiral.[10]

Stereogenic centers

This section has multiple issues. Please help improve it or discuss these issues on the talk page. (Learn how and when to remove these template messages) This section needs additional citations for verification. Please help improve this article by adding citations to reliable sources in this section. Unsourced material may be challenged and removed. (February 2016) (Learn how and when to remove this message) This section may contain information not important or relevant to the article's subject. Please help improve this section. (February 2016) (Learn how and when to remove this message) (Learn how and when to remove this message)

Main article: Stereogenic center

In general, chiral molecules have point chirality at a single stereogenic atom, which has four different substituents. The two enantiomers of such compounds are said to have different absolute configurations at this center. This center is thus stereogenic (i.e., a grouping within a molecular entity that may be considered a focus of stereoisomerism).

Normally, when a tetrahedral atom has four different substituents it is chiral. However, in rare cases, if two of the ligands differ from each other by being mirror images of each other, the mirror image of the molecule is identical to the original, and the molecule is achiral. This is called pseudochirality.

A molecule can have multiple stereogenic centers without being chiral overall if there is a symmetry between the two (or more) stereocenters themselves. Such a molecule is called a meso compound.

It is also possible for a molecule to be chiral without having actual point chirality. Common examples include 1,1'-bi-2-naphthol (BINOL), 1,3-dichloro-allene, and BINAP, which have axial chirality, (E)-cyclooctene, which has planar chirality, and certain calixarenes and fullerenes, which have inherent chirality.

A form of point chirality can also occur if a molecule contains a tetrahedral subunit which cannot easily rearrange, for instance 1-bromo-1-chloro-1-fluoroadamantane and methylethylphenyltetrahedrane.

It is important to keep in mind that molecules have considerable flexibility and thus, depending on the medium, may adopt a variety of different conformations. These various conformations are themselves almost always chiral. When assessing chirality, a time-averaged structure is considered and for routine compounds, one should refer to the most symmetric possible conformation.

When the optical rotation for an enantiomer is too low for practical measurement, it is said to exhibit cryptochirality.

Even isotopic differences must be considered when examining chirality. Replacing one of the two 1H atoms at the CH2 position of benzyl alcohol with a deuterium (2H) makes that carbon a stereocenter. The resulting benzyl-α-d alcohol exists as two distinct enantiomers, which can be assigned by the usual stereochemical naming conventions. The S enantiomer has [α]D = +0.715°.[11][non-primary source needed]

The identity of the stereogenic atom

This section does not cite any sources. Please help improve this section by adding citations to reliable sources. Unsourced material may be challenged and removed. (February 2016) (Learn how and when to remove this message)

The stereogenic atom in chiral molecules is usually carbon, as in many biological molecules. However chirality can exist in any atom, including metals (as in many chiral coordination compounds), phosphorus, or sulfur. Chiral nitrogen is equally possible, although the effects of nitrogen inversion can make many of these compound impossible to isolate.

The chiral atom Carbon Nitrogen Phosphorus (phosphates) Phosphorus (phosphines) Sulfur Metal (type of metal)
1 stereogenic center Serine, glyceraldehyde Cyclanoline Sarin, VX Esomeprazole, armodafinil Tris(bipyridine)ruthenium(II) (ruthenium), cis-Dichlorobis(ethylenediamine)cobalt(III) (cobalt), hexol (cobalt)
2 stereogenic centers Threonine, isoleucine Tröger's base Adenosine triphosphate DIPAMP Dithionous acid
3 or more stereogenic centers Met-enkephalin, leu-enkephalin DNA

In biochemistry

This section has multiple issues. Please help improve it or discuss these issues on the talk page. (Learn how and when to remove these template messages) This section needs additional citations for verification. Please help improve this article by adding citations to reliable sources in this section. Unsourced material may be challenged and removed. (February 2016) (Learn how and when to remove this message) This section may contain information not important or relevant to the article's subject. Please help improve this section. (February 2016) (Learn how and when to remove this message) (Learn how and when to remove this message)

Many biologically active molecules are chiral, including the naturally occurring amino acids (the building blocks of proteins) and sugars. In biological systems, most of these compounds are of the same chirality: most amino acids are L and sugars are D. Typical naturally occurring proteins, made of L amino acids, are known as left-handed proteins, whereas D amino acids produce right-handed proteins.

The origin of this homochirality in biology is the subject of much debate.[12][page needed] Most scientists believe that Earth life's "choice" of chirality was purely random, and that if carbon-based life forms exist elsewhere in the universe, their chemistry could theoretically have opposite chirality. However, there is some suggestion that early amino acids could have formed in comet dust. In this case, circularly polarised radiation (which makes up 17% of stellar radiation) could have caused the selective destruction of one chirality of amino acids, leading to a selection bias which ultimately resulted in all life on Earth being homochiral.[13][full citation needed]

Enzymes, which are chiral, often distinguish between the two enantiomers of a chiral substrate. One could imagine an enzyme as having a glove-like cavity that binds a substrate. If this glove is right-handed, then one enantiomer will fit inside and be bound, whereas the other enantiomer will have a poor fit and is unlikely to bind.

L-forms of amino acids tend to be tasteless, whereas D-forms tend to taste sweet.[12][page needed] Spearmint leaves contain the L-enantiomer of the chemical carvone or R-(–)-carvone and caraway seeds contain the D-enantiomer or S-(+)-carvone.[14] These smell different to most people because our olfactory receptors also contain chiral molecules that behave differently in the presence of different enantiomers.

Chirality is important in context of ordered phases as well, for example the addition of a small amount of an optically active molecule to a nematic phase (a phase that has long range orientational order of molecules) transforms that phase to a chiral nematic phase (or cholesteric phase). Chirality in context of such phases in polymeric fluids has also been studied in this context.[15]

Inorganic chemistry

Delta-ruthenium-tris(bipyridine) cation

Main article: Complex (chemistry): Isomerism

Chirality is a symmetry property, not a characteristic of any part of the periodic table. Thus, many inorganic materials, molecules, and ions are chiral. Quartz is an example from the mineral kingdom. Such noncentric materials are of interest for applications in nonlinear optics.

In the areas of coordination chemistry and organometallic chemistry, chirality is pervasive and of practical importance. A famous example is tris(bipyridine)ruthenium(II) complex in which the three bipyridine ligands adopt a chiral propeller-like arrangement.[16] The two enantiomers of complexes such as [Ru(2,2′-bipyridine)3]2+ may be designated as Λ (capital lambda, the Greek version of "L") for a left-handed twist of the propeller described by the ligands, and Δ (capital delta, Greek "D") for a right-handed twist (pictured).

Chiral ligands confer chirality to a metal complex, as illustrated by metal-amino acid complexes. If the metal exhibits catalytic properties, its combination with a chiral ligand is the basis of asymmetric catalysis.[17]

Stereogenic lone pairs

This section needs additional citations for verification. Please help improve this article by adding citations to reliable sources in this section. Unsourced material may be challenged and removed. (February 2016) (Learn how and when to remove this message)
Inversion of an ammonia molecule at nitrogen. The C3 axis of ammonia is presented as vertical.
 ⇌ 
Inversion of a generic organic amine molecule at nitrogen. The C3 axis of the amine is presented as horizontal, and the pair of dots represent the lone pair of the nitrogen atom collinear with that axis. A mirror plane can be imagined to relate the two amine molecules on either side of the arrows. If the three R groups attached to the nitrogen are all unique, then the amine is chiral; whether it can be isolated depends on the free energy required for the molecule's inversion.

A nonbonding pair of electrons, a lone pair, can contribute to the existence of chirality in a molecule, when three other groups attached to an atom all differ.[citation needed] The effect is seen in certain amines, phosphines,[18][page needed] sulfonium and oxonium ions, sulfoxides, and even carbanions.[citation needed] Chiral phosphines are a further example of molecules displaying such properties as a result of lone pair contributions.[citation needed]

In the case of chiral amines, separation of enantiomers can be difficult, because the energy barrier for nitrogen inversion at the stereo center may be low, which can allow the two stereoisomers to rapidly interconvert at room temperature.[citation needed] As a result, such chiral amines cannot be resolved, unless the amine's groups are constrained in a cyclic structure (such as in Tröger's base),[citation needed] or some other circumstance contributes to an increased barrier to interconversion.[citation needed]

Methods and practices

This section needs expansion with: one or more sections, again with reference to Eliel, describing the methods and tools used in determining structure, generally, and then determining chiroptical properties, and absolute and relative configuration, and methods and tools for characterizing and quantifying enantiomers and diastereomers in mixtures, for resolution and racemization, for studying topicity and prochirality with special emphasis on NMR), and for stereoselective synthesis (stub referencing main article). You can help by adding to it. (February 2016)

The term optical activity is derived from the interaction of chiral materials with polarized light. In a solution, the (−)-form, or levorotatory form, of an optical isomer rotates the plane of a beam of linearly polarized light counterclockwise. The (+)-form, or dextrorotatory form, of an optical isomer does the opposite. The rotation of light is measured using a polarimeter and is expressed as the optical rotation.

Miscellaneous nomenclature

This section may contain unverified or indiscriminate information in embedded lists. Please help clean up the lists by removing items or incorporating them into the text of the article. (February 2016)
This scientific article needs additional citations to secondary or tertiary sources. Help add sources such as review articles, monographs, or textbooks. Please also establish the relevance for any primary research articles cited. Unsourced or poorly sourced material may be challenged and removed. (February 2016) (Learn how and when to remove this message)

Further reading

The following are principle sources for the developing content in this article, that contain further information that may be of interest to readers. In the books listed, the material on chirality appears throughout, and so page numbers should be given for specific ideas and quotations drawn from them that are introduced above.

See also

References

  1. ^ Organic Chemistry (4th Edition) Paula Y. Bruice.[full citation needed]
  2. ^ Organic Chemistry (3rd Edition) Marye Anne Fox ,James K. Whitesell.[full citation needed]
  3. ^ IUPAC, Compendium of Chemical Terminology, 2nd ed. (the "Gold Book") (1997). Online corrected version: (2006–) "Chirality". doi:10.1351/goldbook.C01058
  4. ^ IUPAC, Compendium of Chemical Terminology, 2nd ed. (the "Gold Book") (1997). Online corrected version: (2006–) "Superposability". doi:10.1351/goldbook.S06144
  5. ^ Lakhtakia, A. (ed.) (1990). Selected Papers on Natural Optical Activity (SPIE Milestone Volume 15). SPIE. ((cite book)): |author= has generic name (help)[full citation needed]
  6. ^ Pasteur, L. (1848). "Researches on the molecular asymmetry of natural organic products, English translation of French original, published by Alembic Club Reprints (Vol. 14, pp. 1–46) in 1905, facsimile reproduction by SPIE in a 1990 book". ((cite journal)): Cite journal requires |journal= (help)
  7. ^ "Chirality in Molecules Devoid of Chiral Centers (Chapter 14)". Stereochemistry of Organic Compounds (1st ed.). New York, NY, USA: Wiley & Sons. 1994. ISBN 0471016705. Retrieved 2 February 2016. ((cite book)): Cite uses deprecated parameter |authors= (help) For a further but less stable source of the same text that provides access to the relevant material, see [1], same access date.
  8. ^ Bentley, Ronald (1995). "From Optical Activity in Quartz to Chiral Drugs: Molecular Handedness in Biology and Medicine". Perspect. Biol. Med. 38 (2): 188–229. doi:10.1353/pbm.1995.0069. PMID 7899056. Retrieved 2 February 2016.
  9. ^ IUPAC, Compendium of Chemical Terminology, 2nd ed. (the "Gold Book") (1997). Online corrected version: (2006–) "Optical isomers". doi:10.1351/goldbook.O04308
  10. ^ Cotton, F. A., "Chemical Applications of Group Theory," John Wiley & Sons: New York, 1990.
  11. ^ ^ Streitwieser, A., Jr.; Wolfe, J. R., Jr.; Schaeffer, W. D. (1959). "Stereochemistry of the Primary Carbon. X. Stereochemical Configurations of Some Optically Active Deuterium Compounds". Tetrahedron. 6 (4): 338–344. doi:10.1016/0040-4020(59)80014-4.((cite journal)): CS1 maint: multiple names: authors list (link)[non-primary source needed]
  12. ^ a b Meierhenrich, Uwe J. (2008). Amino acids and the Asymmetry of Life. Berlin, GER: Springer. ISBN 3540768858.[page needed]
  13. ^ McKee, Maggie (2005-08-24). "Space radiation may select amino acids for life". New Scientist. Retrieved 2016-02-05.
  14. ^ Theodore J. Leitereg, Dante G. Guadagni, Jean Harris, Thomas R. Mon, and Roy Teranishi (1971). "Chemical and sensory data supporting the difference between the odors of the enantiomeric carvones". J. Agric. Food Chem. 19 (4): 785–787. doi:10.1021/jf60176a035.((cite journal)): CS1 maint: multiple names: authors list (link)
  15. ^ Srinivasarao, M. (1999). "Chirality and Polymers". Current Opinion in Colloid and Interface Science. 4 (5): 369–376. [full citation needed]
  16. ^ von Zelewsky, A. (1995). Stereochemistry of Coordination Compounds. Chichester: John Wiley.. ISBN 047195599X.[full citation needed]
  17. ^ Hartwig, J. F. Organotransition Metal Chemistry, from Bonding to Catalysis; University Science Books: New York, 2010. ISBN 189138953X
  18. ^ Quin, L. D. (2000). A Guide to Organophosphorus Chemistry, LOCATION: John Wiley & Sons. PAGES. ISBN 0471318248.[full citation needed]
  19. ^ Eliel, E.L. (1997). "Infelicitous Stereochemical Nomenclatures". Chirality. 9: 428–430. Retrieved 5 February 2016.