Non-stabilized transition metal carbenes as intermediates in intramolecular reactions of alkynes with alkenes

In this tutorial review we summarize the two major pathways followed in the reaction of alkenes with alkynes catalysed by electrophilic transition metals. If the metal coordinates simultaneously to the alkyne and the alkene, an oxidative cyclometallation can ensue to give a metallacyclopentene, which usually evolves by beta-hydrogen elimination to give Alder-ene cycloisomerisation derivatives. On the other hand, coordination of the metal to the alkyne promotes the attack of the alkene to give metal cyclopropyl carbenes.