Living Carbonylative Polymerization of Vinylarenes Using <i>P</i> ‐Chirogentic Pd Catalyst: A Route to Functionalized Polyketone with Chirality Recognition

Abstract The enantioselective copolymerization of vinylarenes with carbon monoxide (CO) valorizes C1 resources and upgrades the conventional materials. However, this reaction still suffers from limited molecular weight and narrow polymer functionality, thus restricting chiral application. Here, we present a series of P ‐chirogenic [P,O]‐ligands using chiral amine auxiliary, and demonstrate their applications in Pd‐catalyzed enantioselective copolymerization of diverse vinylarenes with CO. It is discovered that Pd catalyst having significant steric disparity at phosphorus atom displayed up to 99% isotacticity, completely alternating selectivity and head‐to‐tail regularity. The living character enabled the synthesis of enantioenriched block architecture, achieving molecular weight as high as 289 kg/mol. Notably, the fluoro‐containing polyketone films easily processed under mechanical force displayed unexpected chirality recognition toward L‐ and D‐amino acids. The outstanding catalytic performance underlines the powerful asymmetric induction for P ‐chirogenic catalyst in polymerization, and also provides a new avenue to exploit of enantiopure polyketones for developing materials toward chiral separation, sensing, imaging and other functions.