Ring-Opening Metathesis Polymerization of Levoglucosenone-Derived Enyne Monomers

Levoglucosenone (LGO) has emerged as a versatile synthon in target-oriented synthesis due to its availability from cellulose. While its functionality and chirality have found direct use as a small molecule building block, translation to polymerization has been more challenging. Monomers derived from LGO have been difficult to polymerize through conventional chain-growth approaches due to lack of ring strain and steric hindrance. Here, we demonstrate that installation of an alkyne moiety results in a directing group to facilitate the ring-opening metathesis polymerization of LGO-derived monomers. These enyne monomers show controlled polymerization behavior and degrade over the course of weeks under acidic conditions. Additionally, the livingness of the polymerization permits the synthesis of amphiphilic diblock copolymers that can form well-defined micelles in water.