Regioselective and Redox‐Neutral Cp*Ir III ‐Catalyzed Allylic C−H Alkynylation

Herein, we report a Cp*Ir III ‐catalyzed highly regioselective and redox‐neutral protocol for the construction of 1,4‐enynes from unactivated olefins and bromoalkynes via intermolecular allylic C−H alkynylation. The developed mild reaction conditions tolerate a broad range of common functional groups, even enabling selective alkynylation of allylic C−H bonds in the presence of other prominent directing groups. Mechanistic experiments including the isolation of a catalytically active Ir III ‐allyl species support an intermolecular allylic C−H activation followed by an electrophilic alkynylation.