Catalytic Intermolecular Tail‐to‐Tail Hydroalkenylation of Styrenes with α Olefins: Regioselective Migratory Insertion Controlled by a Nickel/N‐Heterocyclic Carbene

Making head or tail of it : The first single‐operation, highly selective intermolecular tail‐to‐tail hetero‐hydroalkenylation from two readily available monosubstituted alkenes is described (see scheme; IPr=1,3‐Bis(2,6‐di‐isopropylphenyl)imidazol‐2‐ylidene). The reaction is catalyzed by the proposed [(IPr)NiH]OTf species. The method allows the use of more common and structurally diverse α olefins as substrates, which were previously not compatible with known methods.