A Single Functionalization Agent for Heterotelechelic ROMP Polymers

Heterotelechelic polymers are an important class of materials finding applications in bioconjugation, imaging, sensing, and synthesis of organic/inorganic hybrid systems with interesting features. However, the synthesis of such polymers is challenging. Here, we report a mechanistically unique and most efficient method based on a single functionalization agent to prepare heterotelechelic polymers by a ring-opening metathesis polymerization. Different functionalization agents can be synthesized in one simple step from inexpensive commercial starting materials. The functionalization agents initially generate a functional initiator from commercial Grubbs’ first-generation ruthenium benzylidene catalyst. During this process, a functional dihydrofuran derivative is produced. After functional initiation and propagation of a suitable monomer, the dihydrofuran derivative functionally terminates the polymerization yielding a primary alcohol-terminated heterotelechelic polymer. Molecular weight control is achieved by varying the ratio between monomer and Grubbs’ first-generation catalyst. This method may emerge as a popular choice to prepare heterotelechelic polymers due to its simplicity and efficiency.