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 intermediate. The Overman rearrangement was discovered in 1974 by Larry Overman.
The [3,3]-sigmatropic rearrangement is diastereoselective and requires heating or the use of Hg(II) or Pd(II) salts as catalysts. The resulting allylamine structures can be transformed into many chemically and biologically important natural and un-natural amino acids (like (1-adamantyl)glycine). The Overman rearrangement may also be used for asymmetric synthesis.
See also Pinner reaction
References
Further reading Isobe, M.; et al. (1990). "Synthetic studies on (−)-tetrodotoxin (3) nitrogenation through overman rearrangement and guanidine ring formation". Tetrahedron Lett. 31 (23): 3327. doi:10.1016/s0040-4039(00)89056-5. Allmendinger, T.; et al. (1990). "Fluoroolefin dipeptide isosteres -II". Tetrahedron Letters. 31 (50): 7301. doi:10.1016/s0040-4039(00)88549-4. Nishikawa, T.; Asai, M.; Ohyabu, N.; Isobe, M. (1998). "Improved Conditions for Facile Overman Rearrangement(1)". J. Org. Chem. 63 (1): 188–192. doi:10.1021/jo9713924. PMID 11674062.