Title：Chemoselectivity Streamlines the Approach to Linear and Y-Shaped Thiol-Polyethers Starting from Thiocarboxylic Acids

Abstract: Thiol-functionalized polyethers, especially poly(ethylene oxide) (PEO), have extensive applications in biomedicine and materials sciences. Herein, we report simple one-pot synthesis of α-thiol-ω-hydroxyl polyethers through ring-opening polymerization (ROP) of epoxides using thiocarboxylic acid initiators followed by in situ aminolysis. The efficient and chemoselective metal-free Lewis pair catalyst avoids transthioesterification thus achieving well-controlled molar mass, low dispersity, and high end-group fidelity.Kinetic and calculation results demonstrated a fast-initiation mode of the ROP for the strong nucleophilicity of the thiocarboxylate anion and its weak interaction with Lewis acid. The method is expanded for α-thiol-ω-dihydroxyl (Y-shaped) PEO in virtue of the stability of thioester during the ROP. The thiol functionality in linear/Y-shaped PEO is further corroborated by the intensified interaction with gold surface and the resultant protein resistance behavior.

DOI：https://doi.org/10.1021/acsmacrolett.3c00407