Electrochemical Total Synthesis of Pyrrolophenanthridone Alkaloids: Controlling for the Anodically Initiated Electron Transfer Process
Electrochemical Total Synthesis of Pyrrolophenanthridone Alkaloids: Controlling for the Anodically Initiated Electron Transfer Process
复制标题
吡咯并菲啶酮生物碱的电化学全合成：控制阳极引发的电子转移过程
DOI：
10.1021/acs.orglett.0c01082
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发表时间：
2020
期刊：
影响因子：
5.2
通讯作者：
Kazuhiro Chiba
中科院分区：
文献类型：
--
作者：
Kazuhiro Okamoto;Kazuhiro Chiba
发展了电化学分子内C（sp2）-H交叉偶联和电化学吲哚合成。这两个反应都是由相同的富电子吲哚啉部分的阳极氧化引发的，但产物的选择性由不同的电子转移过程控制。分子内交叉偶联是通过在MeNO 2-HFIP-LiClO 4体系中产生强亲电自由基阳离子中间体实现的。吲哚的形成是通过苄基氧化和连续去质子化完成的。我们将这些反应应用于天然吡咯并菲酮生物碱的全合成。
Electrochemical intramolecular C(sp2)–H cross-coupling and dehydrogenative indole synthesis were developed. Both reactions were initiated by anodic oxidation of the same electron-rich indoline moiety, but the product selectivity was controlled by different electron-transfer processes. Intramolecular cross-coupling was achieved by the generation of a strong electrophilic radical cation intermediate in the MeNO2–HFIP–LiClO4system. Indole formation was accomplished through benzylic oxidation and continuous deprotonation. We applied these reactions to the total synthesis of natural pyrrolophenanthridone alkaloids.