Acceptorless Dehydrogenative Polymerization

Abstract The development of polymerization strategies for enabling the synthesis of polymeric materials with targeted properties remains a central pursuit at the interface of catalysis, polymer chemistry, and materials science. Acceptor‐less dehydrogenative polymerization (ADP) has emerged as an approach for a step‐growth polymerization for the construction of polyesters, polyamides, polyurethanes, and polyureas from unactivated alcohols and amines, liberating molecular hydrogen as the only by‐product. Mechanistically, ADP represents the macromolecular extension of the x framework, wherein transition‐metal catalysts mediate sequential substrate dehydrogenations and condensations. By leveraging well‐established small‐molecule dehydrogenation chemistry into a repetitive polymer‐forming sequence, ADP unites synthetic efficiency with sustainability to offer access to structurally diverse and high‐performance polymers directly from readily available feedstocks. This minireview highlights the mechanistic foundations, representative catalytic systems, and emerging polymer architectures realized through ADP while identifying some critical challenges and future opportunities we envision will shape its evolution into an enabling platform for green and circular macromolecular design.