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.