The article by Tetsuya Satoh and Masahiro Miura discusses the oxidative coupling of aromatic substrates with alkynes and alkenes under rhodium catalysis, focusing on regioselective C–H bond cleavage. The coordination of oxygen- and nitrogen-containing substituents to the rhodium center is crucial for effective bond activation. Various fused-ring systems can be constructed through these reactions. The authors review the development of this catalytic process, highlighting its advantages over palladium-catalyzed reactions in terms of substrate scope and reaction efficiency. Key examples include the oxidative coupling of benzoic acids, phenols, alcohols, imines, amides, and phenylazoles with alkynes and alkenes, demonstrating the versatility and robustness of the rhodium-catalyzed oxidative coupling. The article also provides plausible mechanisms for several key reactions, emphasizing the role of coordination and reductive elimination steps. Overall, the work showcases the potential of rhodium catalysis in creating π-conjugated molecules from simple, readily available substrates.The article by Tetsuya Satoh and Masahiro Miura discusses the oxidative coupling of aromatic substrates with alkynes and alkenes under rhodium catalysis, focusing on regioselective C–H bond cleavage. The coordination of oxygen- and nitrogen-containing substituents to the rhodium center is crucial for effective bond activation. Various fused-ring systems can be constructed through these reactions. The authors review the development of this catalytic process, highlighting its advantages over palladium-catalyzed reactions in terms of substrate scope and reaction efficiency. Key examples include the oxidative coupling of benzoic acids, phenols, alcohols, imines, amides, and phenylazoles with alkynes and alkenes, demonstrating the versatility and robustness of the rhodium-catalyzed oxidative coupling. The article also provides plausible mechanisms for several key reactions, emphasizing the role of coordination and reductive elimination steps. Overall, the work showcases the potential of rhodium catalysis in creating π-conjugated molecules from simple, readily available substrates.