The rearrangement reaction of α,β-epoxy acylates incyclic systems was studied. The treatment ofcis-derivatives with a Lewis acid afforded rearrangedproducts via the regioselective β-cleavage ofthe oxirane ring due to the electron-withdrawing nature of the acyloxygroup, whereas trans-derivatives enhanced the neighboring group participation to yield only asmall amount of rearrangedproducts. This rearrangement reaction proved to be useful for theconstruction of a variety ofspirocyclane systems or quaternary carbon centers on rings and could beapplied to their synthesesas optically active forms.
