Photoelectrochemical C–H Amination of Guaiacol

Herein, we report a metal-free, photoelectrochemical (PEC) strategy for the direct C–H amination of guaiacol. Using a rationally designed PEC system, we achieved efficient amination with a range of nitrogen nucleophiles, including phenothiazines (PTZs) and phenoxazine (PNX), affording the corresponding products in yields of up to 90%. This operationally simple protocol demonstrates the unique potential of PEC to enable challenging transformations under mild conditions, providing a sustainable route to valuable N-arylamines.