Electrochemical dual α,β-C(sp3)–H functionalization of cyclic N-aryl amines

Abstract

Herein, a straightforward and efficient route for the construction of dual α,β-C(sp³)–H functionalized cyclic N-aryl amines using a combination of electrocatalysis and iron catalysis is disclosed. This method is achieved by multiple single electron oxidations and is carried out in an operationally simple manner with high chemo- and site-selectivity, setting the stage for the challenging multiple site selective C–H functionalization. The mechanism is supported by a variety of experimental probes and theoretical investigations, including cyclic voltammetry tests, a bipolar ultramicroelectrode (BUME) methodology combined with nano-electrospray ionization mass spectrometry, and density functional theory calculations.