The use of metal hydrides (tin, silicon and mercury hydrides) is common in radical cyclization reactions; the primary limitation of this method is the possibility of reduction of the initially formed radical by H-M. Fragmentation methods avoid this problem by incorporating the chain-transfer reagent into the substrate itself—the active chain-carrying radical is not released until after cyclization has taken place. The products of fragmentation methods retain a double bond as a result, and extra synthetic steps are usually required to incorporate the chain-carrying group.
Atom-transfer methods rely on the movement of an atom from the acyclic starting material to the cyclic radical to generate the product. These methods use catalytic amounts of weak reagents, preventing problems associated with the presence of strong reducing agents (such as tin hydride). Hydrogen- and halogen-transfer processes are known; the latter tend to be more synthetically useful.
Oxidative and reductive cyclization methods also exist. These procedures require fairly electrophilic and nucleophilic radicals, respectively, to proceed effectively. Cyclic radicals are either oxidized or reduced and quenched with either external or internal nucleophiles or electrophiles, respectively.