Metal-free ring-opening metathesis polymerization.

We have developed a method to achieve ring-opening metathesis polymerization (ROMP) mediated by oxidation of organic initiators in the absence of any transition metals. Radical cations, generated via one-electron oxidation of vinyl ethers, were found to react with norbornene to give polymeric species with microstructures essentially identical to those traditionally obtained via metal-mediated ROMP. We found that vinyl ether oxidation could be accomplished under mild conditions using an organic photoredox mediator. This led to high yields of polymer and generally good correlation between M(n) values and initial monomer to catalyst loadings. Moreover, temporal control over reinitiation of polymer growth was achieved during on/off cycles of light exposure. This method demonstrates the first metal-free method for controlled ROMP.