Decyanative arylation via radical coupling

Arenes, especially heteroarenes, are crucial structural motifs in organic chemistry, pharmaceutical chemistry, and materials science. The introduction of (hetero)aryl groups using readily available feedstocks to modify organic chemicals is a significant topic. Nitriles are ubiquitous and versatile building blocks in organic synthesis. This article summarizes recent advances in decyanative arylation via radical cross‐coupling reactions. In these transformations, (hetero)aromatic nitriles undergo one‐electron reduction to form persistent radical anion intermediates. Simultaneously, transient carbon centered radicals are generated through cleavage of C–H, C–C, C–X (where X = B, N, Si, S, Br) bonds through single electron transfer or hydrogen atom transfer processes. Finally, a radical‐radical coupling reaction followed by CN elimination leads to the formation of aromatized products.