The Overman rearrangement is a chemical reaction that can be described as a Claisen rearrangement of allylic alcohols to give allylic trichloroacetamides through an imidate intermediate.[1][2][3] The Overman rearrangement was discovered in 1974 by Larry Overman.[4]
The Overman rearrangement
The [3,3]-sigmatropic rearrangement is diastereoselective and requires heating or the use of Hg(II) or Pd(II) salts as catalysts.[5] The resulting allylamine structures can be transformed into many chemically and biologically important natural and un-natural amino acids (like (1-adamantyl)glycine).[6]
The Overman rearrangement may also be used for asymmetric synthesis.[7][8]
^Larry E. Overman (1976). "A general method for the synthesis of amines by the rearrangement of allylic trichloroacetimidates. 1,3 Transposition of alcohol and amine functions". J. Am. Chem. Soc.98 (10): 2901–2910. doi:10.1021/ja00426a038.
^Overman, L. E. (1980). "Allylic and propargylic imidic esters in organic synthesis". Accounts of Chemical Research. 13 (7): 218–224. doi:10.1021/ar50151a005.
^Organic Syntheses, Coll. Vol. 6, p.507; Vol. 58, p.4 (Article Archived 2011-05-14 at the Wayback Machine)
^Overman, L. E. (1974). "Thermal and mercuric ion catalyzed [3,3]-sigmatropic rearrangement of allylic trichloroacetimidates. 1,3 Transposition of alcohol and amine functions". Journal of the American Chemical Society. 96 (2): 597–599. doi:10.1021/ja00809a054.
^Overman, L. E.; Carpenter, N. E. (2005). "The Allylic Trihaloacetimidate Rearrangement". Org. React.66: 1. doi:10.1002/0471264180.or066.01. ISBN 0471264180.
^Chen, Y. K.; Lurain, A. E.; Walsh, P. J. (2002). "A General, Highly Enantioselective Method for the Synthesis of D and L α-Amino Acids and Allylic Amines". Journal of the American Chemical Society. 124 (41): 12225–12231. doi:10.1021/ja027271p. PMID 12371863.
^Anderson, C. E.; Overman, L. E. J. Am. Chem. Soc.2003, 125, 12412–12413. (doi:10.1021/ja037086r)
^Asymmetric Overman RearrangementOrganic Syntheses, Vol. 82, p.134 (2005). (Article Archived 2011-05-14 at the Wayback Machine)
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W X Y Z See also External links 1,2-Wittig rearrangement 1,3-Dipolar cycloaddition 2,3-Wittig rearrangement Abramovitch–Shapiro tryptamine synthesis Acetalisation...
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Mumm rearrangement with transfer of the R4 acyl group from oxygen to nitrogen. All reaction steps are reversible except for the Mumm rearrangement, which...
chemistry during her sophomore year after taking a class with Larry E. Overman, whom she later conducted undergraduate research with. She graduated magna...
Jessup PJ, Petty CB, Roos J, Overman LE (1988). "1-N-Acylamino-1,3-dienes from 2,4-pentadienoic acids by the Curtius rearrangement: benzyl trans-1,3-butadiene-1-carbamate"...
thereafter by Williams,[4] Ganesan,[5] Fuji,[6] Carreira,[7] Horne,[8] Overman,[9] and most recently Trost.[10] From a synthetic point of view, the most...
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imidate intermediate and then undergoes Mumm rearrangement to afford the Passerini product. As the Mumm rearrangement requires a second carboxylic acid molecule...
The transmetalation step is normally the rate-determining step. Larry Overman and coworkers make use of the Stille-carbonylative cross-coupling in their...
aluminium Wilhelm Ostwald (1853–1932), 1909 Nobel Prize in Chemistry Larry E. Overman (born 1943), American organic chemist Geoffrey Ozin (born 1943), materials...
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