Overman rearrangement

From Wikipedia, the free encyclopedia

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] The Overman rearrangement was discovered in 1974 by Larry Overman.[4]

The Overman rearrangement

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).[5]

The Overman Rearrangement also exists as an asymmetric synthesis [6][7]

[edit] References

  1. ^ 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: 2901–2910. doi:10.1021/ja00426a038. 
  2. ^ Overman, L. E. (1980). "Allylic and propargylic imidic esters in organic synthesis". Accounts of Chemical Research 13: 218–224. doi:10.1021/ar50151a005. 
  3. ^ Organic Syntheses, Coll. Vol. 6, p.507; Vol. 58, p.4 (Article)
  4. ^ 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. 
  5. ^ 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. 
  6. ^ Anderson, C. E.; Overman, L. E. J. Am. Chem. Soc. 2003, 125, 12412–12413. (doi:10.1021/ja037086r)
  7. ^ Asymmetric Overman Rearrangement Organic Syntheses, Vol. 82, p.134 (2005). (Article)

[edit] Further reading