Alkyl allyl ethers undergo facile thermally induced isomerization to alkyl l-propenyl ethers in the presence of Group VIII transition metal carbonyl compounds as catalysts. The addition of a silane containing a Si-H bond to these systems results in a catalyst system that is capable of not only isomerizing the allyl ether to the 1-propenyl ether, but further results in the polymerization of these later compounds. High molecular weight polymers can be obtained directly from the alkyl allyl ether in a single step. The scope and limitations of these polymerizations are described.