Catalytic Carbonylation of Dienes to Polyamides with Hydroxylamine as the Nitrogen Source.

Semiaromatic polyamides (SAPs) represent high-performance polymers that have a wide range of applications in the automotive and electronic industries for their exceptional strength and thermomechanical stability. Despite the maturity of existing synthetic techniques, developing a general method for the efficient construction of structurally diverse functional polyamides remains a significant challenge. We herein report a novel polyamidation methodology by carbonylation of hydroxylamine, where the amide joints between diene monomers were forged by relay hydroaminocarbonylation and Lossen rearrangement process. This strategy exhibits high regioselectivity and broad substrate generality, leading to a variety of structurally diverse SAPs with good thermal resistance. Departing from conventional polymerization, this catalytic system circumvents diacids preactivation and transcends the reliance on traditional diamines, which represents a promising alternative for developing advanced polyamide materials.