Iron-catalyzed oxidative etherification of benzylic C(sp3)–H bonds with phenols

[Display omitted] •The first oxidative etherification of benzylic C(sp3)–H bonds with phenols.•A novel straightforward and green approach toward aryl ethers.•A novel strategy for the protection of phenolic hydroxyl groups.•A novel application of iron catalysts and therefore enriches the chemistry of iron catalysis. The first oxidative etherification of benzylic C(sp3)–H bonds with phenols is achieved by using readily available ionic Fe(III) complex [HIPym][FeBr4] as catalyst and DTBP as oxidant. The present work provides a general protocol with high levels of step- and atom-economy for the synthesis of aryl ethers, particularly for aryl benzyl ethers. The direct use of toluene and phenols as starting materials also renders this protocol as a novel strategy for the protection of hydroxyl groups presented in various phenols.