Facile End-Functionalization of Poly(Quinolylene-2,3-Methylene) Using the Terminal Palladium Complex: Thiocarbonylation through Formation of an Acyl Palladium Complex at the Polymer Terminal.

The end-functionalization of poly(quinolylene-2,3-methylene)s (PQM) via thiocarbonylation is successfully achieved by forming an acyl palladium complex. The terminal palladium complex of the PQMs synthesized by living cyclocopolymerization of o-allenylaryl isocyanide is quantitatively converted to a tractable acyl palladium complex through the carbon monoxide insertion into a palladium-carbon bond. The resulting acyl palladium complex exhibits high reactivity toward thiols, thereby enabling the introduction of various substituents at the ω-chain end of PQM by selectively converting them to thioester groups. The one-pot procedure enables the arbitrary control of both terminal structures of PQMs, including the synthesis of multi-armed block copolymers and a triblock polymer. Additionally, the resulting thioester groups can serve as reactive sites and be converted into amide groups using amines. The new end-functionalization method has the potential to be applied not only to the synthesis of PQM but also to other polymerization reactions using transition-metal complexes, and can lead to a wide range of developments in polymer synthesis.