Zirconacyclopentadienes, prepared from two alkynes or a diyne, reacted with the alkyl-, trimethylsilyl-, or alkoxy-substituted third alkyne as well as an alkyne with an electron-withdrawing group in the presence of a stoichiometric amount of NiBr2(PPh3)(2) to give benzene derivatives in good yields. Heteroatom-containing a diynes such as dipropargylbenzylamine and propargyl-homopropargylbenzylamine gave ispindoline and tetrahydroisoquinoline derivatives in good to high yields. This procedure was also used for the selective preparation of benzene derivatives from three different alkynes. The use of trimethylsilyl-substituted alkyne as the first, second or third alkyne afforded desilylated benzene derivatives. The reaction of zirconacyclopentadienes with allenes gave benzene derivatives as a mixture of two isomers.