Geraniol trichloroacetimidate

Thermal and mercury(ii)-catalysed [3,3]sigmatropic rearangement of allylic trichloroacetimidates and allylic pseudo-ureas" e.g. geraniol, linalool) are useful for the 1,3-transposition of hydroxy- and amino-groups the former is synthetically preferred. The [2,3]sigmatropic rearrangement of allylic sulphoxides has been used to effect an alkylative 1,3-carbonyl transposition of enones (e.g. carvone). ... 

Conversion of ailylic alcohols into rearranged allylic amines. This transposition can be accomplished by conversion of an allyhc alcohol, for example geraniol (1), into the trichloroacetimidate (2) by treatment with sodium or potassium hydride and then with trichloroacetonitrile (ether, -10° and then 20°). This allylic imidate undergoes a [3.3] sigmatropic rearrangement when... 

In some cases, the mercury(II)- and palladium(II)-catalysed allylic Overman rearrangement of trichloroacetimidates can be accomplished under mild conditions at room temperature or even much lower temperature. For example, the trichloroacetimidic ester of geraniol 12 is converted to linalyl trichloroacetamide 13 when treated with 0.2 equiv of mercuric trifluoroacetate at room temperature for 10 min. This catalytic... 

---