Glycopolymers Prepared by Ring-Opening Metathesis Polymerization Followed by Glycoconjugation Using a Triazole-Forming "Click" Reaction.

We describe a protocol for the preparation of glycopolymers derived from the ring-opening polymerization of a norbornene carboxylic acid derivative. Polymerization is followed by attachment of a linker and subsequent glycoconjugation via a triazole-forming azide-alkyne click reaction. The use of a protected amine-terminating agent allows for the attachment of a probe molecule such as a fluorescein dye. The syntheses of a neutral galactopolymer as well a polyanionic poly-3-O-sulfo-galactopolymer are described.

End-labeled amino terminated monotelechelic glycopolymers generated by ROMP and Cu(I)-catalyzed azide-alkyne cycloaddition.

Functionalizable monotelechelic polymers are useful materials for chemical biology and materials science. We report here the synthesis of a capping agent that can be used to terminate polymers prepared by ring-opening metathesis polymerization of norbornenes bearing an activated ester. The terminating agent is a cis-butene derivative bearing a Teoc (2-trimethylsilylethyl carbamate) protected primary amine. Post-polymerization modification of the polymer was accomplished by amidation with an azido-amine linker followed by Cu(I)-catalyzed azide-alkyne cycloaddition with propargyl sugars. Subsequent Teoc deprotection and conjugation with pyrenyl isothiocyanates afforded well-defined end-labeled glycopolymers.