Electrochemical Total Synthesis of Pyrrolophenanthridone Alkaloids: Controlling the Anodically Initiated Electron Transfer Process
Kazuhiro Okamoto, Kazuhiro Chiba
Abstract
Electrochemical intramolecular C(sp 2 )–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 MeNO 2 –HFIP–LiClO 4 system. Indole formation was accomplished through benzylic oxidation and continuous deprotonation. We applied these reactions to the total synthesis of natural pyrrolophenanthridone alkaloids.
Topics & Concepts
ChemistryElectrochemistryElectron transferProcess (computing)Combinatorial chemistryElectronChemical engineeringNanotechnologyPhotochemistryElectrodePhysical chemistryComputer scienceOperating systemEngineeringMaterials scienceQuantum mechanicsPhysicsChemical synthesis and alkaloidsOxidative Organic Chemistry ReactionsRadical Photochemical Reactions