A New Class of Amide Ligands Enable Cu‐Catalyzed Coupling of Sodium Methanesulfinate with (Hetero)aryl Chlorides

((2 S ,4 R )‐4‐Hydroxy‐ N ‐(2‐methylnaphthalen‐1‐yl)pyrrolidine‐2‐carboxamide (HMNPC), an amide derived from 4‐hydroxy‐ L ‐proline and 2‐methyl naphthalen‐1‐amine, is a powerful ligand for Cu‐catalyzed coupling of (hetero)aryl halides with sulfinic acid salts, allowing for first time the metal‐catalyzed coupling of (hetero)aryl chlorides and NaSO 2 Me. A considerable number of (hetero)aryl chlorides worked well, providing the pharmaceutically important (hetero)aryl methylsulfones in good to excellent yields.