Diacyl peroxides: practical reagents as aryl and alkyl radical sources

Abstract

Diacyl peroxides, which can be easily synthesized from corresponding carboxylic acids, are commonly utilized as radical initiators and one electron oxidants. Under thermal, transition-metal catalysis or irradiation conditions the cleavage of relatively weak O–O bonds would occur followed by CO₂ extrusion to generate the corresponding aryl or alkyl radicals. Thus, diacyl peroxides can be employed as ideal arylating and alkylating reagents in organic synthesis, including C–H/N–H arylation/alkylation, aryl/alkyl radical addition to unsaturated bonds, hetero arylation/alkylation, eliminative arylation/alkylation, perfluoroalkylation etc. Moreover, these arylation/alkylation protocols have been successfully utilized in the synthesis and late-stage functionalization of natural products as well as bioactive molecules. In this review, recent advances on arylation and alkylation using diacyl peroxides as aryl and alkyl radical sources are summarized and discussed.