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An efficient Cu(I)-catalyzed oxidative cyclization of alkynyl-tethered enynamides for the construction of fused bicyclic cyclopentadiene derivatives is disclosed. The cascade proceeds through alkyne oxidation, carbene/alkyne metathesis, and formal (3 + 2) cycloaddition. Employing aryl-tethered enynamides as starting materials, substituted 2-aminofurans can be exclusively formed.The liquid structures of three alkyl ammonium bromide and urea DESs, ethylammonium bromideurea (11), butylammonium bromideurea (11), and ethylammonium bromide/bu