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 → π 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 acyl-metal intermediates from unactivated primary and secondary amides.