Abstract

AbstractThis article reports on radical arylations, also highlighting the very important early achievements in this field. Included are the Meerwein arylation and the Pschorr reaction. Intramolecular homolytic aromatic substitutions with aryl radicals and various arene radical acceptors for the formation of biaryls are discussed. Along with reactive aryl radicals, nucleophilic and also electrophilic alkyl radicals can cyclize with arenes providing products of intramolecular homolytic aromatic substitution. Discussion on the mechanism is provided. Moreover, it is shown that this chemistry has been successfully used in complex natural‐products synthesis. A section is devoted to radical aryl migration reactions. Finally, reactions of aryl radicals with olefins are discussed. It is also shown that aryl radicals react efficiently with various heteroatom‐based radical acceptors for aryl‐X bond formation (X = Se, S, Te, B, P).

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