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The complex was found to be catalytically active for the <jats:italic>endo<\/jats:italic> cycloisomerization of alkynols. The catalytic reactions can be used to synthesize five\u2010, six\u2010, and seven\u2010membered <jats:italic>endo<\/jats:italic>\u2010cyclic enol ethers in good to excellent yields. A catalytic cycle involving a vinylidene intermediate was proposed for the catalytic reactions. 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