Sustainable Mn‐Assisted Cu‐Catalyzed Cross‐Coupling of Primary Amides and Sulfonamides with (Hetero)Aryl and Styryl Halides: Investigating a Novel Catalytically Active Species

Abstract We report, for the first time, an efficient manganese (Mn)‐assisted copper (Cu)‐catalyzed cross‐coupling reaction that involves a range of aryl, heteroaryl, and styrenyl halides with various primary amides, sulfonamides, and cinnamamide, in air without solvents or added ligands. This cost‐effective protocol successfully produced the desired cross‐coupling products— N ‐aryl and N ‐styryl amides, sulfonamides, and cinnamamides—in good to excellent yields. It demonstrates a broad substrate scope (98 examples) and is tolerant to various sensitive functionalities such as –COCH 3 , –CO 2 Et, –NO 2 , –OH, –NH 2 , –Br, –Cl, –F, –CF 3 , –OCF 3 , –OCH 3 , –CH 2 Ph, and heterocycles. No conventional workup is needed for this protocol, and the developed method is suitable for gram‐scale synthesis. Notably, the catalyst is cost‐effective, environmentally benign, and can be reused at least five times with minimal loss of catalytic activity. This protocol demonstrates a lower E‐factor and PMI value compared to other methods, indicating its sustainability and benignity. Several experiments, including X‐ray photoelectron spectroscopy (XPS), powder X‐ray diffraction (PXRD), and scanning electron microscopy (SEM), were carried out to identify the catalytically active species based on Mn–Cu and their oxidation state. Additionally, a radical clock experiment was performed using a radical probe to investigate the reaction mechanism, and a novel Mn–Cu‐based catalytic cycle for this transformation has been proposed.