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