Abstract The addition of a series of both aliphatic and aromatic amines to electron‐poor olefins was investigated using [Ni( Pigiphos )(THF)] 2+ as catalyst (with different counterions) in various ionic liquids based on imidazolium‐ and picolinium‐salt derivatives. The catalysts gave rise to selectivities comparable to those obtained when the reaction was conducted in neat organic solvents (ee up to 66%), but significant higher activities, with a total turnover number (TON) of up to 300.
