Shape-selective C–H activation of aromatics to biarylic compounds using molecular palladium in zeolites

The selective activation of inert C–H bonds has emerged as a promising tool for avoiding the use of wasteful traditional coupling reactions. Oxidative coupling of simple aromatics allows for a cost-effective synthesis of biaryls. However, utilization of this technology is severely hampered by poor regioselectivity and by the limited stability of state-of-the-art homogeneous Pd catalysts. Here, we show that confinement of cationic Pd in the pores of a zeolite allows for the shape-selective C–H activation of simple aromatics without a functional handle or electronic bias. For instance, out of six possible isomers, 4,4′-bitolyl is produced with high shape selectivity (80%) in oxidative toluene coupling on Pd-Beta. Not only is a robust, heterogeneous catalytic system obtained, but this concept is also set to control the selectivity in transition-metal-catalysed arene C–H activation through spatial confinement in zeolite pores. Controlling the regioselectivity in the coupling of simple aromatics is challenging. Now, para–para selectivity is achieved during the aerobic dehydrogenative homocoupling of arenes through a shape-selective catalyst based on molecular palladium confined within the framework of zeolite materials.