Exploring Remote C─H Bond Arylation: Transition Metal Catalysis Without “End‐On Template”

ABSTRACT C─H bond functionalization has appeared as one of the most efficient tools for building complex molecular scaffolds. Despite growing interest in remote C─H bond functionalization, achieving the distal site selectivity is highly challenging. Traditional “end‐on template” based methods usually require additional steps for installing and removing long directing templates, and often rely on expensive transition metals, which makes the process less sustainable. In this essay, an alternative concept known as “complementary catalysis” is discussed to achieve remote C─H arylation without the use of large templates. This approach requires a small directing group to control regioselectivity under mild conditions without any externally added ligands or activators. Most importantly, it paves a more sustainable route by improving the atom and step economy.