Functionalized aliphatic polycarbonates have emerged as promising biocompatible materials for use in drug delivery, polymer-based therapeutics, and imaging contrast agents. Much of this research has focused on functionalized cyclic carbonate monomers that can undergo ring-opening polymerization by cationic, anionic, coordination-insertion, organocatalytic, and enzymatic methods. We have developed several new families of organic catalysts that rival or exceed metal-based alternatives for polycarbonate synthesis, both in terms of activity and selectivity. Critically, the successful application of aliphatic polycarbonates in the biomedical field stems from unprecedented ease in which many desired functionalities can be introduced. Significant effort has been devoted to develop facile strategies to incorporate functionality at both the monomer level and post-polymerization by the judicious combination of orthogonal coupling chemistries. In particular, cyclic carbonate monomers and subsequents polymerization having pendant ester, amide, or thioester functional groups based on 2,2-bis(hydroxymethyl)propionic acid have been reported.<br/><br/>The synthesis of cyclic carbonate monomers having a pendent pentafluorophenyl ester group enabled a diverse library of functional groups, this monomer was synthisized in a single step from commercially available bis(hydroxymethyl)propionic acid. Combining the diiol, pentaflourophenyl carbonate and CsF effectively cyclized two hydroxyl groups while concurrently activating the ester with a pendent pentafluorophenyl carbonate. Using nucleophiles such as alcohols, amines and thiols, a library of functional monomers was rapidly generated. These monomers were polymerized using organocatalysis yielding new degradable polymers having many possible pendent groups.

Functional polycarbonates: A broadly useful biodegradable polymer platform

251st National Meeting (2016)

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