The directed ortho metalation—cross coupling symbiosis. Regioselective methodologies for biaryls and heterobiaryls. Deployment in aromatic and heteroaromatic natural product synthesis

In this mini-review, synthetic methods for biaryls and heterobiaryls interconnecting the directed ortho metalation (DoM) reaction with Corriu–Kumada, Negishi, Suzuki–Miyaura and, less, Stille cross coupling reactions are presented from perspectives of development of new reaction parameters (Suzuki–Miyaura: Scheme 4, Scheme 5, Scheme 6 and Scheme 7), new cross coupling partners (Corriu–Kumada: Scheme 9 and Scheme 11), and comprehensive evaluation ( Scheme 12 and Scheme 13). Recent work on the application of these protocols to indole derivatives ( Scheme 16, Scheme 17 and Scheme 18), dibenzopyranones ( Scheme 19), aza- and isoazacoumestans ( Scheme 20), and kinamycin antibiotics ( Scheme 21) is described.