Bioinspired Electrochemical Cyclization toward the Divergent Synthesis of Mavacurane- and Akuammiline-Type Alkaloids.

We report a divergent electrochemical strategy for the bioinspired synthesis of mavacurane- and akuammiline-type alkaloid frameworks from a common indole-malonate precursor. By tuning the redox mediator, selective N-C or C-C bond formation was achieved. Iodide-mediated electrolysis promoted iodination of the malonate carbanion, followed by intramolecular nucleophilic cyclization to furnish the mavacurane core. In contrast, ferrocene-mediated oxidation generated a malonate-centered radical that afforded the akuammiline skeleton.