Palladium-Catalyzed Homo- and Copolymerization of Polar Monomers: Synthesis of Aliphatic and Aromatic Polymers

Transition-metal-catalyzed coordinationinsertion polymerization of olefins is an indispensable tool in polymer synthesis. When polar monomers with polar functional groups are employed, however, the catalysts are often deactivated owing to side reactions such as σ-coordination and β-elimination of the functional group. Nevertheless, recent progress in late transition metal catalysis has enabled the synthesis of many types of functional polymers from polar monomers through coordinationinsertion polymerization methods. This account describes our achievements in the palladium-catalyzed coordinationinsertion (co)polymerization of polar monomers for the syntheses of a variety of functional polymers, ranging from functionalized polyolefins via olefin/polar monomer copoly-merization to o-arylene-containing polymers via formal aryne polymerization.