Ligand-Controlled Nickel-Catalyzed Tandem Isomerization/Regiodivergent Hydroheteroarylation of α-Alkenes with Heteroarenes.

We herein describe an accessible ligand-controlled nickel-catalyzed tandem isomerization/regiodivergent hydroheteroarylation of α-alkenes with a series of heteroarenes, wherein the NHC ligand of heteroleptic Ni(II) complexes of the type Ni(NHC)[P(OEt) 3 ]Br 2 displayed significant effects on regulation. In the presence of NaO t Bu, Ni(IMes)[P(OEt) 3 ]Br 2 enables C═C bond isomerization of α-alkenes over up to four sp 3 carbon atoms to afford branched products, while Ni(IPr* OMe )[P(OEt) 3 ]Br 2 greatly deactivates α-alkene isomerization and favors the formation of linear products.