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)]Br displayed significant effects on regulation. In the presence of NaOBu, Ni(IMes)[P(OEt)]Br enables C═C bond isomerization of α-alkenes over up to four sp carbon atoms to afford branched products, while Ni(IPr*)[P(OEt)]Br greatly deactivates α-alkene isomerization and favors the formation of linear products.