ABSTRACT
Cyclic saturated or unsaturated dialkylperoxides are termed endoperoxides with 1,2-dioxetanes as exceptions that are normally not grouped in the endoperoxide family.
The prefix
endo
has only historical reasons
and by no means indicates stereochemical properties, thus the term “
exo
peroxides” should be avoided. Common useage also comprises monocyclic dialkylperoxides and bi-and polycyclic compounds. The central structural feature determining the thermal, the photochemical, and also the redox behavior of endoperoxides is the oxygen-oxygen single bond. In most thermal or photochemical processes, homolytic OO bond cleavage follows activation; redox processes are mostly initiated by one-electron reduction followed by mesolytic cleavage or a subsequent secondary electron transfer.
