Strategies for the reductive cycloaddition of enals or enoates with alkynes have been developed. The enal-alkyne cycloaddition directly affords cyclopentenols, whereas the enoate-alkyne cycloaddition affords the analogous cyclopentenones. The mechanism of these processes likely involves formation and protonation of a metallacyclic intermediate. The general strategy provides a straightforward entry to five-membered ring products from simple, stable pi-systems.