Photoinduced EDA Complexes Enabled C(sp²)-OMe Bond Cleavage and Cyanation of Electron-Rich Arenes

Herein, an EDA complex enabling C(sp²)-OMe bond cleavage and cyanation was established by using 1,4-dicyanobenzene as both an electron-deficient acceptor and a low-toxicity cyanide source. Mechanistic studies revealed the role of double EDA complexes in forming the cyanide anion and aromatic cation radical intermediate, leading to a diverse array of valuable aryl nitrile derivatives in good to excellent yields. Furthermore, late-stage functionalization of biorelevant compounds and gram-scale synthesis demonstrate the utility of this methodology.