N-Methylamino Pyrimidyl Amides (MAPA): Highly Reactive, Electronically-Activated Amides in Catalytic N-C(O) Cleavage

Despite recent progress in catalytic cross coupling technologies, the direct activation of N-alkyl-N-aryl amides has been a challenging transformation. Here, we report the first Suzuki cross-coupling of N-methylamino pyrimidyl amides (MAPA) enabled by the controlled n(N) -> pi(Ar), conjugation and the resulting remodeling of the partial double bond character of the amide bond. The new mode of amide activation is suitable for generating aryl-metal intermediates from unactivated primary and secondary amides.