Department of Chemistry, Brown University, Providence, Rhode Island 02912, USA.
Beilstein J Org Chem. 2013 Mar 25;9:608-12. doi: 10.3762/bjoc.9.66. Print 2013.
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.
功能化的单端聚合物是化学生物学和材料科学领域的有用材料。我们在此报告了一种封端剂的合成方法，该封端剂可用于终止通过开环易位聚合制备的带有活性酯的降冰片烯聚合物。封端剂是一种带有 Teoc（2-三甲基硅乙基碳酸氨基乙酯）保护的伯胺的顺丁烯衍生物。通过与叠氮基-胺接头进行酰胺化，然后进行 Cu(I)-催化的叠氮化物-炔烃环加成反应与丙炔基糖，完成了聚合物的后聚合修饰。随后 Teoc 的脱保护作用和与芘基异硫氰酸酯的缀合作用，得到了结构明确的末端标记糖聚合物。
