Laboratorium für Organische Chemie, ETH Zürich, Vladimir-Prelog-Weg 3, HCI, 8093, Zürich, Switzerland.
Angew Chem Int Ed Engl. 2023 Jan 23;62(4):e202214071. doi: 10.1002/anie.202214071. Epub 2022 Dec 20.
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.
报道了一种铑催化的芳香族和脂肪族末端炔烃的反马氏规则氢碘加成反应。根据配体和底物的选择，可以高立体选择性地得到（E）-或（Z）-构型的烯基碘化物。该反应具有广泛的底物范围和高官能团容忍性，通过穿梭过程，使用易得或商业可得的脂肪族碘化物作为 HI 替代物。合成的乙烯基碘化物在几种 C-C 和 C-杂原子键形成反应中得到了应用，立体选择性完全保留。该方法可用于显著缩短海洋顺式脂肪酸的全合成。此外，初步的氘标记实验和计量反应揭示了潜在的反应机理。
