Electrochemical Regioselective Phosphorylation of Nitrogen‐Containing Heterocycles and Related Derivatives

The site‐selective functionalization of biologically important nitrogen‐containing heterocycles and related derivatives remains a challenging and important task. We report herein on the direct regiodivergent N1/C2 phosphorylation of free indole derivatives. Cyclic voltammograms and EPR data indicate that by utilizing different electrolyte‐mediated anodic oxidation to generate different active indole species, a diverse collection of N1 and C2 phosphorylation products could be obtained in moderate to high yields under exogenous‐oxidant‐free and metal‐catalyst‐free electrochemical conditions. In addition, N−P coupling was also found to be compatible with various alkylamines.