Total syntheses of codonopsinine and 4-epi-codonopsinine via gold-mediated tandem catalyzed pyrrole synthesis
Total syntheses of codonopsinine and 4-epi-codonopsinine via gold-mediated tandem catalyzed pyrrole synthesis
复制标题
金介导串联催化吡咯合成全合成党参碱和4-表党参碱
DOI：
10.1038/ja.2016.13
复制
发表时间：
2016
期刊：
影响因子：
--
通讯作者：
H. Tokuyama
中科院分区：
文献类型：
--
作者：
M. Yamaguchi;D. Itagaki;H. Ueda;H. Tokuyama
完成了参dopopsinine(1)和4-epi参dopopsinine(2)的全合成。通过金催化的氨基乙醛缩醛衍生物和末端炔的加成-环化级联反应，构建了键取代吡咯中间体。将吡咯中间体用锌粉和磺酸非对映选择性还原为相应的3-吡咯啉衍生物后，通过二羟基化对二醇进行立体选择性构建，得到了4-外延参嘌呤(2)的全合成。此外，codonopsinine(1)的全合成是在酸性水溶液条件下，通过环氧化物将羟基立体转化，然后进行环解理完成的。
The total syntheses of codonopsinine (1) and 4-epi-codonopsinine (2) were accomplished. The key substituted pyrrole intermediate was constructed via gold-catalyzed addition–cyclization cascade of an aminoacetaldehyde acetal derivative and a terminal alkyne. After diastereoselective reduction of the pyrrole intermediate to the corresponding 3-pyrroline derivative with zinc dust and sulfonic acid, the total synthesis of 4-epi-codonopsinine (2) was achieved via stereoselective construction of the diol by dihydroxylation. In addition, the total synthesis of codonopsinine (1) was completed through stereochemical inversion of the hydroxyl group via epoxide and subsequent ring cleavage under the acidic aqueous condition.