Alternating Cascade Metathesis Polymerization of Enynes and Cyclic Enol Ethers with Active Ruthenium Fischer Carbenes

Ruthenium alkoxymethylidene complexes have rarely been demonstrated as active species in metathesis reactions and are frequently regarded as inert. Herein, we highlight the ability of these Fischer-type carbenes to participate in cascade alternating ring-opening metathesis polymerization through their efficient alkyne addition reactions. When enyne monomers are combined with low-strain cyclic vinyl ethers, a controlled chain-growth copolymerization occurs that exhibits high degrees of alternation (>90% alternating diads) and produces degradable poly(vinyl ether) materials with low dispersities and targetable molecular weights. This new method is amenable to the synthesis of alternating diblock polymers that can be degraded to small-molecule fragments under aqueous acidic conditions. This work furthers the potential of Fischer-type ruthenium alkylidenes in polymerization strategies and presents new avenues for the generation of functional metathesis materials.