Nickel(0)‐Catalyzed Hydrocyanation of Terminal Allenes: A Regio‐ and Enantioselective Approach to Branched Allylic Nitriles

A highly branched regioselective nickel(0)-catalyzed hydrocyanation of mono- and 1,1-disubstituted allenes as well an asymmetric are reported herein, giving access to tertiary quaternary β,γ-allylic nitriles. For the terminal allenes, a nickel(0)/Biphephos catalytic system applicable substrate scope containing functional groups such ester, THP-group, primary aliphatic iodide, free carboxylic acid, provides yields up 96%. By applying Ni(0)/TADDOL-based bisphosphite catalyst allylic nitriles obtained in 99% enantioselectivities 86%. Both protocols take advantage manageable HCN source evidence good atom economy. In addition, reaction's synthesis utility is highlighted by gram-scale reactions with subsequent assorted transformation nitrile group alkylation α-position.