Sauvage Center for Molecular Sciences, Engineering Research Center of Organosilicon Compounds & Materials (Ministry of Education), College of Chemistry and Molecular Sciences, Wuhan University, Wuhan, 430072, China.
College of Chemistry and Chemical Engineering, Hunan University, Changsha, 410082, China.
Angew Chem Int Ed Engl. 2021 Mar 1;60(10):5141-5146. doi: 10.1002/anie.202014660. Epub 2021 Jan 18.
Reported here is a concise total synthesis of (-)-berkelic acid in eight linear steps. This synthesis features a Catellani reaction/oxa-Michael cascade for the construction of the isochroman scaffold, a one-pot deprotection/spiroacetalization operation for the formation of the tetracyclic core structure, and a late-stage Ni-catalyzed reductive coupling for the introduction of the lateral chain. Notably, four stereocenters are established from a single existing chiral center with excellent stereocontrol during the deprotection/spiroacetalization process. Stereocontrol of the intriguing deprotection/spiroacetalization process is supported by DFT calculations.
本文报道了 (-)-berkelic 酸的简洁全合成，共 8 步线性步骤。该合成方法的特点是通过 Catellani 反应/氧杂-Michael 级联反应构建异色满骨架，一锅脱保护/螺缩酮化反应形成四环核心结构，以及在后期通过 Ni 催化的还原偶联反应引入侧链。值得注意的是，在脱保护/螺缩酮化过程中，通过单个现有手性中心建立了四个立体中心，具有极好的立体控制。有趣的脱保护/螺缩酮化过程的立体控制得到了 DFT 计算的支持。
