Carbonylative Aminative Suzuki-Miyaura Coupling: Pd-Catalyzed Synthesis of Amides from Vinyl/Aryl Halides and Boronic...

Amide synthesis is critical for the development of pharmaceuticals, agrochemicals, and functional materials. Here, we report a four-component variant of the Pd-catalyzed Suzuki-Miyaura coupling that repurposes partners conventionally used for C-C bond formation to instead yield amides. The sequential insertion of CO, from Mo(CO)₆ as a convenient surrogate, and NH, from O-(diphenylphosphinyl)hydroxylamine (DPPH), allows access to a broad scope of secondary amides bearing aromatic and olefinic groups, including enamides, α,β-unsaturated amides, and α,β-unsaturated enamides. Drug-like analogs can be rapidly assembled, and we show that "reverse amide" counterparts can be generated from the same starting materials.