The ability of intramolecular anodic olefin coupling reactions to form new carbon-carbon bonds has been shown to depend on the polarization of the intermediate radical cation rather than how electron-rich it is. A series of substrates was studied that allowed for a direct comparison of these two parameters. The successful cyclizations led to the formation of highly functionalized bicyclic molecules containing four contiguous stereogenic atoms, one of which was tetra substituted. For the first time, an ene diol ether derivative was shown to be compatible with the cyclization reaction.