Fe-Catalyzed\nFluoroalkyl(hetero)arylation of Vinyl\nAzaarenes: Rapid and Modular Synthesis of Unsymmetrical 1,1-Bis(hetero)arylalkanes

In contrast to transition-metal-catalyzed difunctionalization\nof\nactivated alkenes, selective alkylarylation of vinyl azaarenes is\nunderdeveloped. Consequently, the lack of modular and rapid syntheses\nof 1,1-bis(hetero)arylalkanes limits their exploration in medicinal\nchemistry. Herein we report a protocol using commercially available\niron salts, bisphosphine ligands, fluoroalkyl halides, and Grignard\nreagents that enables the selective 1,2-fluoroalkyl(hetero)arylation\nof vinyl azaarenes. We demonstrate the versatility and robustness\nof the method through the selective synthesis of a range of unsymmetrical\n1,1-bis(hetero)arylalkenes, including pyridine <i>N</i>-oxides,\ntriazoles, pyrazines, carbazoles, indazoles, and 1,2-azaborines. Mechanistic\ninsights from experimental and computational investigations support\na radical pathway and provide insights into the role of non-covalent\ninteractions in iron catalysis.