State Key Laboratory and Institute of Elemento-organic Chemistry, College of Chemistry, and Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Nankai University, Tianjin, 300071, China.
Angew Chem Int Ed Engl. 2019 Jan 21;58(4):1174-1177. doi: 10.1002/anie.201812822. Epub 2018 Dec 20.
A scalable enantioselective total synthesis of (-)-goniomitine has been developed by using an iridium-catalyzed asymmetric hydrogenation of an exocyclic enone ester to control the configuration of the molecule. The synthesis begins from commercially available starting materials, and proceeds through an integrated asymmetric ketone hydrogenation, Johnson-Claisen rearrangement, and one-pot oxidation/deprotection/cyclization process. With this highly efficient and scalable strategy, (-)-goniomitine was synthesized in eleven steps with 27 % overall yield, and formal enantioselective syntheses of (+)-1,2-dehydroaspidospermidine, (+)-aspidospermidine, and (+)-vincadifformine were also achieved.
已开发出一种可扩展的对映选择性全合成（-）-钩吻素甲的方法，该方法通过使用铱催化的非环烯酮酯的不对称氢化来控制分子的构型。该合成从商业可得的起始原料开始，经过集成的不对称酮氢化、Johnson-Claisen 重排和一锅氧化/脱保护/环化过程进行。通过这种高效且可扩展的策略，以 27%的总收率，经过 11 步反应合成了（-）-钩吻素甲，并实现了（+）-1,2-脱氢阿朴菲啶、（+）-阿朴菲啶和（+）-长春弗林的形式对映选择性合成。
