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Overman rearrangement



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 intermedate.[1][2][3][4] The Overman rearrangement was discovered in 1974 by Larry Overman.[5]

The [3,3]-sigmatropic rearrangement is diastereoselective and can be catalyzed by heat, Hg(II), or Pd(II). 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 also exists as an asymmetric synthesis [7][8]

References

  1. ^ Overman, L. E. J. Am. Chem. Soc. 1976, 98, 2901.
  2. ^ Overman, L. E. J. Am. Chem. Soc. 1976, 98, 2901.
  3. ^ Overman, L. E. (1980). "Allylic and propargylic imidic esters in organic synthesis". Accounts of Chemical Research 13: 218 - 224. doi:10.1021/ar50151a005.
  4. ^ Organic Syntheses, Coll. Vol. 6, p.507; Vol. 58, p.4 (Article)
  5. ^ 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: 597 - 599. doi:10.1021/ja00809a054.
  6. ^ 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: 12225–12231. doi:0.1021/ja027271p.
  7. ^ Anderson, C. E.; Overman, L. E. J. Am. Chem. Soc. 2003, 125, 12412–12413. (doi:10.1021/ja037086r)
  8. ^ Asymmetric Overman Rearrangement Organic Syntheses, Vol. 82, p.134 (2005). (Article)

Further reading

  • Isobe, M. et al. Tetrahedron Lett. 1990, 31, 3327.
  • Allmendinger, T. et al. Tetrahedron Letters 1990, 31, 7301.
  • Nishikawa, T.; Asai, M.; Ohyabu, N.; Isobe, M.; J. Org. Chem. 1998, 63(1), 188-192. (PMID: 11674062)
 
This article is licensed under the GNU Free Documentation License. It uses material from the Wikipedia article "Overman_rearrangement". A list of authors is available in Wikipedia.
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