Visible-Light Copper Nanocluster Catalysis for the C–N Coupling of Aryl Chlorides at Room Temperature

Activation of aryl chlorides in cross-coupling reactions is a long-standing challenge in organic synthesis that is of great interest to industry. Ultrasmall (<3 nm), atomically precise nanoclusters (NCs) are considered one of the most promising catalysts due to their high surface area and unsaturated active sites. Herein, we introduce a copper nanocluster-based catalyst, [Cu₆₁(S^tBu)₂₆S₆Cl₆H₁₄] (Cu₆₁NC) that enables C-N bond-forming reactions of aryl chlorides under visible-light irradiation at room temperature. A range of N-heterocyclic nucleophiles and electronically and sterically diverse aryl/hetero chlorides react in this new Cu₆₁NC-catalyzed process to afford the C-N coupling products in good yields. Mechanistic studies indicate that a single-electron-transfer (SET) process between the photoexcited Cu₆₁NC complex and aryl halide enables the C-N-arylation reaction.