Jing Jing, Hu Ying, Tian Zhenfeng, Wang Yicheng, Yao Liqin, Qiu Lipeng, Ackermann Lutz, Karaghiosoff Konstantin, Li Jie
Key Laboratory of Organic Synthesis of Jiangsu Province, MOE Key Laboratory of Geriatric Diseases and Immunology, Suzhou Key Laboratory of Pathogen Bioscience and Anti-infective Medicine, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, 215123, Suzhou, China.
School of Life Science and Health Engineering, Jiangnan university, 214122, Wuxi, China.
Angew Chem Int Ed Engl. 2024 Oct 21;63(43):e202408211. doi: 10.1002/anie.202408211. Epub 2024 Sep 17.
A palladium-catalyzed highly C-S-selective Stille cross-coupling between aryl thianthrenium salts and tri- or tetrasubstituted alkenyl stannanes is described. Herein, critical challenges including site- and chemoselectivity control are well addressed through C-H thianthrenation and C-S alkenylation, thereby providing an expedient access to stereodefined tri- and tetrasubstituted alkenes in a stereoretentive fashion. Indeed, the palladium-catalyzed Stille-alkenylation of poly(pseudo)halogenated arenes displays privileged capability to differentiate C-S over C-I, C-Br, C-Cl bonds, as well as oxygen-based triflates (C-OTf), tosylates (C-OTs), carbamates and sulfamates under mild reaction conditions. Sequential and multiple cross-couplings via selective C-X functionalization should be widely applicable for increasing functional molecular complexity. Modular installation of stereospecific alkene motifs into pharmaceuticals illustrated the synthetic application of the present protocol in drug discovery.
本文描述了一种钯催化的芳基噻蒽鎓盐与三取代或四取代烯基锡烷之间高度C-S选择性的Stille交叉偶联反应。在此，通过C-H噻蒽化和C-S烯基化很好地解决了包括位点和化学选择性控制在内的关键挑战，从而以立体保持的方式提供了一种便捷地获得立体定义的三取代和四取代烯烃的方法。实际上，钯催化的聚（伪）卤代芳烃的Stille-烯基化反应在温和的反应条件下表现出区分C-S键与C-I、C-Br、C-Cl键以及基于氧的三氟甲磺酸酯（C-OTf）、对甲苯磺酸酯（C-OTs）、氨基甲酸酯和氨基磺酸酯的特殊能力。通过选择性C-X官能化进行的连续和多重交叉偶联应广泛适用于增加功能分子的复杂性。将立体特异性烯烃基序模块化安装到药物中说明了本方案在药物发现中的合成应用。
