LAUSR

The majority of C–C coupling reactions between arenes and olefins result in the formation of branched isomer products, exhibiting what is known as Markovnikov selectivity. However, alternative catalytic strategies are required to modulate this selectivity, thereby yielding linear isomer products that are crucial for various significant applications. In this study, a straightforward Ni0–N‐heterocyclic carbene (NHC) catalyst is presented for the anti‐Markovnikov hydroarylation of unactivated olefins with arenes (benzene) and heteroarenes (pyridine, indole, and imidazopyridine derivatives). The active catalyst species are in situ generated from NHC ligands and a stable NiII salt that is reduced by an alkaline hydride (NaH, LiH). This strategy circumvents the elaborate procedures that have been employed to synthesize and isolate Ni0–NHC complexes. The assessment of >15 reactions between olefins and (hetero)arenes shows the formation of linear isomers as the predominant products, with yields ranging from moderate to excellent and exceptional selectivity.