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Antarafacial ( Woodward-Hoffmann symbol a) and suprafacial (s) are two topological concepts in organic chemistry describing the relationship between two simultaneous
chemical bond A chemical bond is a lasting attraction between atoms or ions that enables the formation of molecules and crystals. The bond may result from the electrostatic force between oppositely charged ions as in ionic bonds, or through the sharing o ...
making and/or bond breaking processes in or around a reaction center. The reaction center can be a p- or sp''n-''orbital (Woodward-Hoffmann symbol ω), a
conjugated system In theoretical chemistry, a conjugated system is a system of connected p-orbitals with delocalized electrons in a molecule, which in general lowers the overall energy of the molecule and increases stability. It is conventionally represented a ...
(π) or even a
sigma bond In chemistry, sigma bonds (σ bonds) are the strongest type of covalent chemical bond. They are formed by head-on overlapping between atomic orbitals. Sigma bonding is most simply defined for diatomic molecules using the language and tools of sy ...
(σ). * The relationship is ''antarafacial'' when opposite faces of the π system or isolated orbital are involved in the process (think ''anti''). For a σ bond, it corresponds to involvement of one "interior" lobe and one "exterior" lobe of the bond. * The relationship is ''suprafacial'' when the same face of the π system or isolated orbital are involved in the process (think ''syn''). For a σ bond, it corresponds to involvement of two "interior" lobes or two "exterior" lobes of the bond. The components of all pericyclic reactions, including
sigmatropic reaction A sigmatropic reaction in organic chemistry is a pericyclic reaction wherein the net result is one σ-bond is changed to another σ-bond in an uncatalyzed intramolecular reaction. The name ''sigmatropic'' is the result of a compounding of the l ...
s and cycloadditions, and electrocyclizations, can be classified as either suprafacial or antarafacial, and this determines the stereochemistry. In particular, antarafacial topology corresponds to inversion of configuration for the carbon atom of a
, ''n'' The comma is a punctuation mark that appears in several variants in different languages. It has the same shape as an apostrophe or single closing quotation mark () in many typefaces, but it differs from them in being placed on the baseline ...
sigmatropic rearrangement, and conrotation for electrocyclic ring closure, while suprafacial corresponds to retention and disrotation. An example is the ,3hydride shift, in which the interacting
frontier orbital A frontier is the political and geographical area near or beyond a boundary. A frontier can also be referred to as a "front". The term came from French in the 15th century, with the meaning "borderland"—the region of a country that fronts o ...
s are the
allyl In organic chemistry, an allyl group is a substituent with the structural formula , where R is the rest of the molecule. It consists of a methylene bridge () attached to a vinyl group (). The name is derived from the scientific name for garlic, . ...
free radical and the hydrogen 1s orbitals. The suprafacial shift is symmetry-forbidden because orbitals with opposite algebraic signs overlap. The symmetry allowed antarafacial shift would require a strained transition state and is also unlikely. In contrast a symmetry allowed and suprafacial ,5hydride shift is a common event.F.A. Carey, R.J. Sundberg, ''Advanced Organic Chemistry'' Part A {{ISBN, 0-306-41087-7


References

Stereochemistry