20.8:
Radical Reactivity: Overview
The unpaired electron makes radicals a highly reactive species.
Consequently, radicals undergo three forms of reactions to achieve stability:
first, by combining with another radical and forming a spin‐paired molecule;
second, by reacting with another spin‐paired molecule to generate a new radical and a new spin‐paired molecule;
third, by decomposing in a unimolecular reaction to form a new radical and a spin‐paired molecule.
These three possible reactions lead to six common steps in radical mechanisms: homolysis, addition to a π bond, hydrogen abstraction, halogen abstraction, elimination, and coupling.
These steps can be categorized into the initiation, propagation, and termination stages of a typical radical mechanism.
Generally, radical reactivity is governed by steric hindrance and electronic stabilization, with electron‐donating and withdrawing groups making radicals nucleophilic and electrophilic, respectively.
20.8:
Radical Reactivity: Overview
Radicals, the highly reactive species, gain stability by undergoing three different reactions. The first reaction involves a radical-radical coupling, in which a radical combines with another radical, forming a spin‐paired molecule. The second reaction is between a radical and a spin‐paired molecule, generating a new radical and a new spin‐paired molecule. The third reaction is radical decomposition in a unimolecular reaction, forming a new radical and a spin‐paired molecule. These three possible reactions result in six different arrow-pushing patterns in radical mechanisms, such as homolysis, addition to a π bond, hydrogen abstraction, halogen abstraction, elimination, and coupling. These six patterns can be categorized into three typical steps, initiation, propagation, and termination, of a radical mechanism. Typically, these radical reactions are governed by two key factors: steric hindrance and electronic stabilization.