Palladium-Catalyzed Intermolecular Asymmetric Hydroamination with 4,4′-Disubstituted BINAP and SEGPHOS

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.