Anodic oxidations and polarity: exploring the chemistry of olefinic radical cations

The cyclization chemistry of radical cations derived from electron-rich olefins has been examined and the relationship between the polarization of the radical cation and the chemoselectivity of the reaction probed. It was found that more polarized radical cations favor carbon-carbon bond formation while less polarized radical cations favor carbon-heteroatom bond formation. A new approach to the synthesis of quaternary carbons was uncovered and the compatibility of ene diol ethers with anodic olefin coupling reactions examined.