In Situ Synthesis of CuN₄/Mesoporous N‐Doped Carbon for Selective Oxidative Crosscoupling of Terminal Alkynes under Mild Conditions

Abstract The 1,3‐conjugated diynes are an important class of chemical intermediates, and the selective crosscoupling of terminal alkynes is an efficient chemical process for manufacturing asymmetrical 1,3‐conjugated diynes. However, it often occurs in homogenous conditions and costs a lot for reaction treatment. Herein, a copper catalyzed strategy is used to synthesize highly ordered mesoporous nitrogen‐doped carbon material (OMNC), and the copper species is in situ transformed into the copper single‐atom site with four nitrogen coordination (CuN₄). These features make the CuN₄/OMNC catalyst efficient for selective oxidative crosscoupling of terminal alkynes, and a wide range of asymmetrical and symmetrical 1,3‐diynes (26 examples) under mild conditions (40 °C) and low substrates ratio (1.3). Density functional theory (DFT) calculations reveal that the aryl–alkyl crosscoupling has the lowest energy barrier on the CuN₄ site, which can explain the high selectivity. In addition, the catalyst can be separated and reused by simply centrifugation or filtration. This work can open a facile avenue for constructing single‐atom loaded mesoporous materials to bridge homogeneous and heterogeneous catalysis.