Experimental Strategies for Controlling Radical Chain Reactions

Free-radical chain reactions have been a mainstay of organic chemistry for many years due to the unique chemical behavior of highly reactive radical species. Recently, there has been a surge of interest in utilizing free-radical chain processes in the development of new synthetic methods for a variety of C–H functionalizations. Robust and reliable synthetic methods demand control, or at the very least, mediation of reactive species that are generated during radical chain processes. In the context of reaction optimization for intermolecular reactions, several recent experimental strategies for controlling the rates of radical initiation and propagation are discussed.