Radical reactions in synthesis

Abstract

This chapter uses the term “radical”, which is an atom or molecule that possesses one or more unpaired electrons and focuses on reactions where useful yields are obtained using radical processes in a solution. It analyzes radical reactions that proceed by a chain mechanism and a crucial initiation step that requires the generation of radicals from an appropriate precursor. It also deals with the main types of reaction which lead to the production of radicals, such as the thermal and photochemical cleavages of compounds with weak bonds and electron transfer processes. The chapter discusses compounds that contain relatively weak bonds with bond dissociation energies (BDE) that undergo homolysis at a convenient rate. It describes the diacylperoxides as an important group of compounds wherein the already weak bond of a simple peroxide is further weakened by resonance stabilization of the acyloxy radical.