Nickel/α‐diimine catalysts in C (sp²)–C (sp²) homocoupling: An underestimated and versatile ligand family

Application of α‐diimine ligands in Ni‐catalyzed reductive homocoupling of haloarenes is reported. The Ni/α‐diimine catalysts are shown to be highly active and allow for preparation of a broad scope of biaryls, including practically important cyclization and polycondensation products. The synthetic availability and versatility of α‐diimines allows for easy tuning of their structure aimed at achieving higher yields of each specific homocoupling product.