The Overman rearrangement is a

chemical reaction A chemical reaction is a process that leads to the chemistry, chemical transformation of one set of chemical substances to another. When chemical reactions occur, the atoms are rearranged and the reaction is accompanied by an Gibbs free energy, ...

that can be described as a

Claisen rearrangement The Claisen rearrangement is a powerful carbon–carbon chemical bond, bond-forming chemical reaction discovered by Rainer Ludwig Claisen. The heating of an allyl Vinyl group, vinyl ether will initiate a Sigmatropic reaction, ,3sigmatropic r ...

allylic In organic chemistry, an allyl group is a substituent with the structural formula . It consists of a methylene bridge () attached to a vinyl group (). The name is derived from the scientific name for garlic, . In 1844, Theodor Wertheim isolat ...

alcohols to give allylic trichloroacetamides through an

imidate Carboximidates (or more general imidates) are organic compounds, which can be thought of as esters formed between an imidic acid () and an Alcohol (chemistry), alcohol, with the general formula . They are also known as imino ethers, since they ...

intermediate. The Overman rearrangement was discovered in 1974 by

Larry Overman Larry E. Overman is Distinguished Professor of Chemistry at the University of California, Irvine. He was born in Chicago in 1943. Overman obtained a B.A. degree from Earlham College in 1965, and he completed his Ph.D. in chemistry from the Unive ...

The ,3sigmatropic rearrangement is

diastereoselective 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 ...

and requires heating or the use of Hg(II) or Pd(II) salts as catalysts. The resulting allylamine structures can be transformed into many chemically and biologically important natural and un-natural amino acids (like (1-

adamantyl Adamantane is an organic compound with formula C10H16 or, more descriptively, (CH)4(CH2)6. Adamantane molecules can be described as the fusion of three cyclohexane rings. The molecule is both rigid and virtually stress-free. Adamantane is the mo ...

)glycine). The Overman rearrangement may also be used for

asymmetric synthesis Enantioselective synthesis, also called asymmetric synthesis, is a form of chemical synthesis. It is defined by IUPAC as "a chemical reaction (or reaction sequence) in which one or more new elements of chirality are formed in a substrate molecul ...

.''Asymmetric Overman Rearrangement'' ''

Organic Syntheses ''Organic Syntheses'' is a peer-reviewed scientific journal that was established in 1921. It publishes detailed and checked procedures for the synthesis of organic compounds. A unique feature of the review process is that all of the data and expe ...

'', Vol. 82, p.134 (2005).
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)

See also

References

Further reading