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 BuOK by ether solvents is crucial, allowing the BuO anion to coordinate with the catalyst's Al center, thus forming a key intermediate.