Aryl nitriles and aryl thioethers are often found in biologically active molecules such as natural products, pharmaceuticals, fragrances, and agrochemicals. (1−4) Notably, these two functional groups are complementary in terms of their reactivity and directing ability for aromatic functionalization chemistry. The CN group is a traditional electron-withdrawing group that deactivates an aromatic ring and directs electrophilic aromatic substitution to the meta position.