Rapid Functionalization of Polycarbonates and Polyurethanes via Organocatalyzed SNAr

Abstract

Robust methodologies for polymer postsynthesis functionalization enable preparation of new high-performance material scaffolds with uniquely tailored properties. Here we demonstrate that polycarbonates containing pendant fluoroarene groups provide a convenient handle for incorporation of different functional thiols into the polymer backbone via organocatalytic nucleophilic aromatic substitution using silyl-protected thiols. This transformation proceeds under mild conditions and can be performed in a single pot immediately following polymerization or on purified substrates in a second step. In both cases, the transformation is typically complete within 5 min. Overall, the methodology presented herein enables a more convergent approach for development of functional high-performance materials.