Nickel‐Catalyzed Decarbonylative Borylation of Amides: Evidence for Acyl C—N Bond Activation.

A nickel/N-heterocyclic carbene catalytic system has been established for decarbonylative borylation of amides with B2nep2 by C−N bond activation. This transformation shows good functional-group compatibility and can serve as a powerful synthetic tool for late-stage borylation of amide groups in complex compounds. More importantly, as a key intermediate, the structure of an acyl nickel complex was first confirmed by X-ray analysis. Furthermore, the decarbonylative process was also observed. These findings confirm the key mechanistic features of the acyl C−N bond activation process.