Reusable, Efficient Manganese–Copper‐Catalyzed Cross‐Coupling of Aryl Halides with Aromatic Alcohols under Solvent‐Minimized Conditions

Abstract We report an efficient ligand‐free manganese–copper‐catalyzed cross‐coupling reaction of differently substituted aryl halides (chlorides, bromides, and iodides) with various aromatic alcohols, conducted under solvent‐minimized conditions. This cost‐effective method efficiently produces the desired cross‐coupling products (diaryl ethers) in good to excellent yields, showcasing a broad substrate scope (65 examples) and tolerance to many sensitive functional groups such as ─CN, ─CHO, ─COOH, ─COCH 3 , ─CO 2 Et, ─SO 2 NH 2 , ─NH 2 , ─NO 2 , ─CH═CH 2 , and heterocycles. No conventional work‐up is essential for this protocol, and the established method is useful for gram‐scale synthesis. Importantly, the catalyst is environmentally friendly, inexpensive, and can be reused at least seven times with insignificant loss of catalytic activity. Several experiments, including X‐ray photoelectron spectroscopy (XPS), X‐ray diffraction (XRD), and UV spectroscopy, were carried out to identify the oxidation state of active catalytic species. Additionally, a radical clock experiment using a radical probe was performed to investigate the reaction mechanism.