Abstract
Enynes are important synthetic intermediates that are also found in a variety of natural products and other biologically relevant molecules. The most atom economical synthetic route to enynes is via the direct coupling of readily available terminal alkyne precursors. Towards this goal, we demonstrate the formation of 1,3-enynes from terminal alkynes facilitated by a reduced ZrIV/Co−I heterobimetallic complex. An intermediate is trapped as a tBuNC adduct, revealing that bimetallic activation of the terminal C–H bond of the alkyne is an essential mechanistic step.