Asymmetric rearrangement reactions are one of the perfect tools for the construction of new carbon-carbon bonds in an enantioselective manner. The enantioselective [2,3]-Wittig rearrangement of cinnamyloxycyclohexanone derivatives, catalyzed by a commercially available primary amine, provided α-hydroxy ketones with high diastereo-and enantioselectivity. A new and straightforward procedure for the synthesis of cinnamyloxycyclohexanone derivatives was developed.