A novel and practical method for the synthesis of diverse α-aryl and α-vinyl nitriles was developed via an iron-catalyzed sp 3 C–O ether bond cleavage with C–C bond formation in the reaction of π-activated ethers with TMSCN. ... Direct cyanation of π-activated ethers to synthesis of α-aryl and α-vinyl nitriles via iron-catalyzed sp 3 C–O ether bond cleavage was developed. ... Selected examples of biologically active α-aryl nitriles. Selected examples of biologically ...