Despite their instability, carbon-centered radicals have been involved as intermediates in many organic transformations that are essential to mankind. Radical polymerization,1-5 for example, provides a large part of polyacrylates and polystyrenes used as commodities in our everyday life. On a molecular level, the outcome of radical-mediated reactions is usually very different from those obtained via classical ionic based organic reactions. This is known since the 1930’s6 and has witnessed extensive developments such as radical cyclization or Atom Transfer Radical Additions (ATRA)7-9 . Radical processes10 typically begin with an initiation step in which the first radical species is created. It is eventually followed by one or several transfer steps which ultimately conduct to the formation of the main radical intermediate responsible for the reaction. The propagation steps of the radical chain are a succession of radical based transformations which, combined, outline the expected transformation.
Supplementary Info ATRAvf