Introducing SuFEx click chemistry into aliphatic polycarbonates: a novel toolbox/platform for post-modification as biomaterials

Abstract

As a biodegradable and biocompatible biomaterial, aliphatic polycarbonates (APCs) have attracted substantial attention in terms of post-polymerization modification (PPM) for functionalization. A strategy for the introduction of sulfur(VI)-fluoride exchange (SuFEx) click chemistry into APCs for PPM is proposed for the first time in this work. 4′-(Fluorosulfonyl)benzyl 5-methyl-2-oxo-1,3-dioxane-5-carboxylate (FMC) was designed as a SuFEx clickable cyclic carbonate for APCs via ring-opening polymerization (ROP), and an operational and nontoxic synthetic route was achieved. FMC managed to undergo both ROP and PPM through the SuFEx click chemistry organocatalytically without constraining or antagonizing each other, using 1,5,7-triazabicyclo[4,4,0]dec-5-ene (TBD) as a co-organocatalyst here. Its ROP was systematically investigated, and density functional theory (DFT) calculations were performed to understand the acid–base catalytic mechanism in the anionic ROP. Exploratory investigations into PPM by SuFEx of poly(FMC) were conducted as biomaterials, and the one-pot strategies to achieve both ROP and SuFEx were confirmed.