Generation of aryl radicals by redox processes. Recent progress in the arylation methodology

Abstract

Arylation methods based on the generation and use of aryl radicals have been a rapidly growing field of research in recent years and currently represent a powerful strategy for carbon – carbon and carbon – heteroatom bond formation. The progress in this field is related to advances in the methods for generation of aryl radicals. The currently used aryl radical precursors include aryl halides, aryldiazonium and diaryliodonium salts, arylcarboxylic acids and their derivatives, arylboronic acids, arylhydrazines, organosulfur(II, VI) compounds and some other compounds. Aryl radicals are generated under mild conditions by single electron reduction or oxidation of precursors induced by conventional reagents, visible light or electric current. A crucial role in the development of the radical arylation methodology belongs to photoredox processes either catalyzed by transition metal complexes or organic dyes or proceeding without catalysts. Unlike the conventional transition metal-catalyzed arylation methods, radical arylation reactions proceed very often at room temperature and have high functional group tolerance. Without claiming to be exhaustive, this review covers the most important advances of the current decade in the generation and synthetic applications of (het)aryl radicals. Examples of reactions are given and mechanistic insights are highlighted. The bibliography includes 341 references.