-Selective Acyclic Diene Metathesis Polymerization of ,-Dienes.

The / stereochemistry of repeating alkenes in polymers provides a powerful handle to modulate the thermal and mechanical properties of these soft materials, but synthetic methods to precisely dictate this parameter remain scarce. We report herein a -selective acyclic diene metathesis (ADMET) polymerization of readily available α,ω-diene monomers with high functional group tolerance. Identification of a highly stereoselective cyclometalated Ru catalyst allowed the synthesis of a broad array of polymers with contents up to 99%.

Stereocontrolled acyclic diene metathesis polymerization.

The cis/trans geometry of olefins is known to dramatically influence the thermal and mechanical properties of polyalkenamers. Yet, polymerization methods that efficiently control this parameter are scarce. Here we report the development of a stereoretentive acyclic diene metathesis polymerization that uses the reactivity of dithiolate Ru carbenes combined with cis monomers.