In general, radical cyclization to produce small rings is difficult. However, it is possible to trap the cyclized radical before re-opening. This process can be facilitated by fragmentation (see the three-membered case below) or by stabilization of the cyclized radical (see the four-membered case). Five- and six-membered rings are the most common sizes produced by radical cyclization.
Polycycles and macrocycles can also be formed using radical cyclization reactions. In the former case, rings can be pre-formed and a single ring closed with radical cyclization, or multiple rings can be formed in a tandem process (as below). Macrocyclizations, which lack the FMO requirement of cyclizations of smaller substrates, have the unique property of exhibiting endo selectivity.