Rhodium-Catalyzed Anti-Markovnikov Transfer Hydroiodination of Terminal Alkynes** |
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Authors: | Philip Boehm Niklas Kehl Prof Dr Bill Morandi |
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Institution: | Laboratorium für Organische Chemie, ETH Zürich, Vladimir-Prelog-Weg 3, HCI, 8093 Zürich, Switzerland |
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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. |
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Keywords: | Anti-Markovnikov Selectivity Hydrofunctionalization Rhodium Shuttle Catalysis Vinyl Iodides |
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