Copper-Catalyzed Allylic C-H Alkynylation by Cross-Dehydrogenative Coupling

C-H bond functionalization is a well-developed concept that has been thoroughly studied and gives entry to rather complex molecules without the need for previous derivatization of the substrates. The use of copper complexes in allylic C-H bond functionalization under oxidative conditions as an alternative to the well-established palladium-based methodologies remains largely underdeveloped. Here, we show for the first time a selective cross-dehydrogenative coupling reaction between underivatized allylic substrates and terminal alkynes to produce 1,4-enynes in high yields in a single step, using an in situ synthesized copper catalyst and an oxidant.