Primary amines as heterogeneous catalysts in an enantioselective [2,3]-Wittig rearrangement reaction

Abstract

A series of heterogeneous catalysts anchored to different polystyrene-based supports has been prepared and applied in an asymmetric [2,3]-Wittig rearrangement reaction of cyclohexanone derivatives. Among them, primary amino acid-derived (aminomethylated)polystyrene-supported catalysts showed excellent reactivity leading to the formation of rearranged products in good enantioselectivities of both diastereomers. Reusability issues connected to the deactivation of the catalyst were proved to be dependent on the end-capping strategy chosen for the blocking of the unreacted active sites of the resin. This issue of end-capping has not previously been in focus. Using bulkier pivaloyl end-capping moiety, we were able to recycle the catalyst in six consecutive cycles with only marginal deceleration of the reaction. Moreover, the epimerization of the product that occurred while conducting a rearrangement reaction in the presence of a homogeneous catalyst was almost fully eliminated by switching the catalytic system to heterogeneous.