Nickel-Catalyzed Migratory Hydrocyanation of Internal Alkenes: Unexpected Diastereomeric-Ligand-Controlled Regiodivergence.

We herein report a regiodivergent nickel-catalyzed hydrocyanation of a broad range of internal alkenes involving the chain-walking process. When appropriate diastereomeric biaryl diphosphite ligands are applied, the same starting materials can be converted to either linear or branched nitriles with good yields and high regioselectivities. DFT calculations suggested that the catalyst architecture determines the regioselectivity via modulating electronic and steric interactions. In addition, moderate enantioselectivities were observed when branched nitriles were delivered.