Overman rearrangement

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The Overman rearrangement is a chemical reaction that can be described as a Claisen rearrangement of allylic alcohols to give allylic trichloroacetamides.[1][2][3][4] The Overman rearrangement was discovered in 1974 by Larry Overman.[5]

The Overman rearrangement
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).[6]

Variations

Asymmetric Overman Rearrangement

[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. (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 Check |doi= value (help). Unknown parameter |coauthors= ignored (help)
  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 readings

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