Ball‐Milling‐Enabled Pd‐Catalyzed One‐Pot  Cross‐Coupling of Aryl Thianthrenium Salts With In Situ Generated Reformatsky Enolates

Mechanochemistry enables an efficient Pd‐catalyzed cross‐coupling of aryl thianthrenium salts with in situ generated Reformatsky‐type enolates. Ball milling plays a dual role by promoting both the activation of zinc to form Reformatsky‐type organozinc enolates from α ‐halo esters and amides and their subsequent cross‐coupling with solid aryl thianthrenium salts. This single‐step one‐pot protocol provides access to a broad range of α ‐arylated products in high yields within short reaction times. The mechanochemical process is performed under ambient conditions without requiring an inert atmosphere, highlighting its operational simplicity and practicality. Furthermore, the methodology is readily applicable to the late‐stage functionalization of structurally complex bioactive molecules.