Rhodium‐Catalyzed Anti‐Markovnikov Transfer Hydroiodination of Terminal Alkynes**

Abstract A rhodium‐catalyzed anti‐Markovnikov hydroiodination of aromatic and aliphatic terminal alkynes is reported. Depending on the choice of ligand and substrate, either ( E )‐ or ( Z )‐configured alkenyl iodides are obtained in high to exclusive isomeric purity. The reaction exhibits a broad substrate scope and high functional group tolerance, employing easily accessible or commercially available aliphatic iodides as HI surrogates through a shuttle process. The synthesized vinyl iodides were applied in several C−C and C−heteroatom bond‐forming reactions with full retention of the stereoselectivity. The developed method could be used to significantly shorten the total synthesis of a marine cis ‐fatty acid. Additionally, initial deuterium‐labeling experiments and stoichiometric reactions shed some light on the potential reaction mechanism.