Tuning reactivity and chemoselectivity in electron transfer initiated cyclization reactions: applications to carbon-carbon bond formation.

In this communication, we demonstrate that the scope of our electron transfer initiated cyclization reaction can be significantly broadened by exploiting the relationship between the oxidation potentials of homobenzylic ethers and the mesolytic benzylic carbon-carbon bond dissociation energies of their radical cations. By lowering the oxidation potential of the electrophore and the benzylic carbon-carbon bond dissociation energy, we can initiate reactions under mild, nonphotochemical conditions. The selectivity of the arene oxidation and the mild reaction conditions allow a variety of electron-rich olefins to serve as nucleophilic groups to form carbon-carbon bonds with excellent efficiency.