Electroreductive Remote Benzylic C(sp3)–H Arylation of Aliphatic Ethers Using Cyanoarenes for the Synthesis of α‑(Hetero)aryl Ethers

An iodoarene-driven electroreductive remote C­(sp3)–H arylation of unsymmetrical 1-(o-iodoaryl)­alkyl ethers with cyanoarenes for the site selective synthesis of α-(hetero)­aryl ethers is developed. With the introduction of cyanoarenes as both aryl sources and electron transfer mediators, this method includes an iodoarene-driven strategy to enable the regiocontrollable formation of two new bonds, one C­(sp2)–H bond, and one C­(sp2)–C­(sp3) bond, in a single reaction step through the sequence of halogen atom transfer (XAT), hydrogen atom transfer (HAT), radical–radical coupling, and decyanation.