Lipp Alexander, Ferenc Dorota, Gütz Christoph, Geffe Mario, Vierengel Nina, Schollmeyer Dieter, Schäfer Hans J, Waldvogel Siegfried R, Opatz Till
Johannes Gutenberg-Universität, Institut für Organische Chemie, Duesbergweg 10-14, 55128, Mainz, Germany.
Westfälische Wilhelms-Universität, Institut für Organische Chemie, Corrensstraße 40, 48149, Münster, Germany.
Angew Chem Int Ed Engl. 2018 Aug 20;57(34):11055-11059. doi: 10.1002/anie.201803887. Epub 2018 Jun 14.
The biosynthesis of thebaine is based on the regioselective, intramolecular, oxidative coupling of (R)-reticuline. For decades, chemists have sought to mimic this coupling by using stoichiometric oxidants. However, all approaches to date have suffered from low yields or the formation of undesired regioisomers. Electrochemistry would represent a sustainable alternative in this respect but all attempts to accomplish an electrochemical synthesis of thebaine have failed so far. Herein, a regio- and diastereoselective anodic coupling of 3',4',5'-trioxygenated laudanosine derivatives is presented, which finally enables electrochemical access to (-)-thebaine.
蒂巴因的生物合成基于（R）-网状番荔枝碱的区域选择性分子内氧化偶联。几十年来，化学家们一直试图通过使用化学计量的氧化剂来模拟这种偶联反应。然而，迄今为止所有方法都存在产率低或形成不需要的区域异构体的问题。在这方面，电化学将是一种可持续的替代方法，但迄今为止所有实现蒂巴因电化学合成的尝试均告失败。在此，我们报道了3',4',5'-三氧化劳丹诺辛衍生物的区域和非对映选择性阳极偶联反应，这最终实现了通过电化学方法获得（-）-蒂巴因。
