Abstract: | A family of tunable precatalysts [Pd((S)‐L*)(NCMe)2](OTf)2, where L* is 4,4′‐disubstituted BINAP or SEGPHOS, was synthesized and used for the asymmetric intermolecular hydroamination of aniline to vinylarenes with ee values of up to 85 %, and it is believed that the bulky groups on the 4,4′‐positions and the narrower dihedral angle of the biaryl moiety are responsible for the ee enhancement in these reactions. |