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.