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Overman rearrangement

From Wikipedia, the free encyclopedia

TheOverman rearrangement is achemical reaction that can be described as aClaisen rearrangement ofallylic alcohols to give allylic trichloroacetamides through animidate intermediate.^[1]^[2]^[3] The Overman rearrangement was discovered in 1974 byLarry Overman.^[4]

The[3,3]-sigmatropic rearrangement isdiastereoselective and requires heating or the use ofHg(II) orPd(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 forasymmetric 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 theWayback 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 ofD andL 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 theWayback Machine)