A general means for enhancing the extent to which squarate esters enter into cascade processes involving a dianionic oxy-Cope rearrangement as the key step is presented. Adoption of this sigmatropic process requires that the two alkenyllithium reagents being introduced add cis to each other, a kinetic bias which can be realized simply by the proper incorporation of ethereal oxygen substituents in the first organometallic reagent. Structural reorganization occurs via boat-like transition states such that stereoinduction manifests itself with high fidelity.