Rhodium‐Catalyzed Anti‐Markovnikov Transfer Hydroiodination of Terminal Alkynes

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.