One-Pot Heterotelechelic Metathesis Polymers via Regioselective Chain Transfer Agents

Single chain transfer agents are used to synthesize narrowly distributed heterotelechelic ROMP polymers in one pot, exploiting a new mechanistic and synthetic approach. The chain transfer agents carrying different functional groups are synthesized in a few straightforward steps. Prefunctionalization of commercially available Grubbs' third-generation catalyst is realized in situ using regioselective chain transfer agents within a short reaction period. After monomer consumption, the excess chain transfer agent in the reaction medium automatically end-functionalizes the polymer chain, yielding a heterotelechelic polymer via a ring-opening-ring-closing sequence. ¹H NMR, MALDI-ToF, and SEC analyses confirmed end-group functionalization as well as excellent control over molecular weight and dispersity. This strategy highlights a new way of synthesizing one-pot heterotelechelic ROMP polymers straightforwardly and efficiently.