[Ir (cod) Cl] 2/DPPE was found to be a new catalyst for the cycloaddition of α, ω-diynes with monoynes to give polysubstituted benzene derivatives in high yields. Internal monoynes as well as terminal monoynes could be used. The reaction tolerates a broad range of functional groups such as alcohol, amine, alkene, ether, halogen, and nitrile. The reaction of 1, 6- octadiyne derivatives with 1-alkynes gives ortho products and meta products. The ...