Aluminum-catalyzed anti-Markovnikov hydroamination of aromatic alkenes with aromatic amines

Herein, we report a novel Al compound supported by a NacNac ligand that facilitates the anti-Markovnikov hydroamination of aromatic alkenes and primary amines. This represents the first instance of an aluminum-catalyzed intermolecular hydroamination of alkenes, successfully synthesizing a variety of aromatic imine derivatives. The proposed mechanism suggests that the coordination activation of tBuOK by ether solvents is crucial, allowing the tBuO- anion to coordinate with the catalyst's Al center, thus forming a key intermediate.