Direct Synthesis of Polyaryls by Consecutive Oxidative Cross-Coupling of Phenols with Arenes

A bioinspired iron-catalyzed consecutive oxidative cross-coupling reaction between a single phenolic unit and nucleophilic arenes was developed. This sustainable transformation offers a selective synthetic strategy for the preparation of complex polyaryl compounds directly from readily available phenols. With the aid of electron paramagnetic resonance spectroscopy, it was demonstrated that the groups ortho to the phenolic functionality (whether hydrogen, methyl, or methoxy) direct the regioselectivity (ortho, para, or meta via dienone–phenol rearrangement) and chemoselectivity (C–C coupling or C–O coupling) in this multistep process.