Synthesis of Clickable Isotactic Poly(vinyl ether)s through Organocatalytic Stereoselective Cationic Copolymerization

Abstract By virtue of the high reliability of click chemistry, polymers with clickable groups provide a useful platform for the rapid synthesis of polymer materials with diverse functionalities and architectures. However, the polymerization of clickable vinyl monomers with a concurrent regulation on tacticity remains underdeveloped. Herein, we report the successful development of a stereoselective cationic copolymerization of C−C triple bond‐containing vinyl ethers with simple alkyl vinyl ethers by employing confined Brønsted acid as catalyst, which allows for the synthesis of alkyne‐functionalized vinyl ether copolymers with high isotacticity (up to 90 % m ), controlled molecular weight, and variable content of C−C triple bonds. Further transformation of the pendant clickable alkyne groups via thiol‐yne click reactions and copper(I)‐catalyzed alkyne‐azide cycloaddition reaction enables a modular access to isotactic polymers with various functional groups.