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Abstract

Alkenyl and aryl peroxides are a special class of organic peroxides. Under ambient conditions, they are usually short‐lived, rapidly decomposing into radicals by homolytic O−O bond cleavage. They play an important role in the chemistry of the lower atmosphere, where they are formed through ozonolysis of alkenes. In the dark, this pathway is considered the major source of hydroxyl radicals, the “detergent of the atmosphere”. In solution, alkenyl and aryl peroxides can be formed by various methods and their decomposition can be harnessed synthetically. For example, reactions involving alkenyl peroxides can be used to introduce ketones through radical additions, and nucleophilic aromatic substitution reactions generating aryl peroxides have been used to synthesize phenols. The radicals can also initiate radical polymerization reactions or chain reactions and mediate oxidative coupling by C−H bond functionalization. Knowledge of their chemistry could be helpful for projects generating or utilizing peroxides.