Functionalizable Stereocontrolled Cyclopolyethers by Ring‐Closing Metathesis as Natural Polymer Mimics

Whereas complex stereoregular cyclic architectures are commonplace in biomacromolecules, they remain rare in synthetic polymer chemistry, thus limiting the potential to develop synthetic mimics or advanced materials for biomedical applications. Herein we disclose the formation of a stereocontrolled 1,4‐linked six‐membered cyclopolyether prepared by ring‐closing metathesis (RCM). Ru‐mediated RCM, with careful control of the catalyst, concentration, and temperature, selectively affords the six‐membered‐ring cyclopolymer. Under optimized reaction conditions, no metathetical degradation, macrocycle formation, or cross‐linking was observed. Post‐polymerization modification by dihydroxylation afforded a novel polymer family encompassing a poly(ethylene glycol) backbone and sugar‐like functionalities (“PEGose”). This strategy also paves the way for using RCM as an efficient method to synthesize other stereocontrolled cyclopolymers.