Nickel-catalyzed aminocarbonylation of aryl chlorides enabled by a newly designed CO source

Transition metal-catalyzed aminocarbonylation of aryl halides represents one of the most direct methods for synthesizing benzamides, a process which plays a pivotal role in a wide range of disciplines including chemistry, biology, medicine, and materials science. While recent advances have achieved more focus on aryl iodides and aryl bromides with palladium as the catalyst, the use of nickel as the catalyst in carbonylation of aryl chlorides remains challenging. Here, we report a nickel-catalyzed aminocarbonylation that overcomes this limitation, including more challenging aryl chlorides substituted with electron-donating groups. The success of this protocol is contingent on the use of inositol hexaformate as a newly developed CO surrogate. Control experiments with CO gas show that inositol hexaformate could release CO gradually in the reaction, avoiding nickel catalytic deactivation. This approach not only accomplishes a series of aminocarbonylation of aryl chlorides, but also provides a new arena for nickel-catalyzed carbonylation.