Overman Rearrangement

L. E. Overman, J. Am. Chem. Soc. 96, 597 (1974); 98, 2901 (1976).

Formal [3,3]-sigmatropic rearrangement of the trichloroacetimidate of allylic alcohols to allylic trichloroacetamides, thereby transposing the hydroxyl and amino functions with good chirality transfer:



Early review: L. E. Overman, Accts. Chem. Res. 13, 218-224 (1980). Synthetic applications: M. Isobe et al., Tetrahedron Letters 31, 3327 (1990); T. Allmendinger et al., ibid. 7301; J. Gonda et al., Synthesis 1993, 729; C. G. Cho et al., Synth. Commun. 30, 1643 (2000). Use of a chiral template and mechanistic studies: T. Eguchi et al., Tetrahedron 49, 4527 (1993). Modification of reaction conditions: T. Nishikawa et al., J. Org. Chem. 63, 188 (1998). Cf. Claisen Rearrangement.