Metal-catalyzed cross-coupling reactions belong to the most important transformations in organic synthesis. Copper catalysis has received great attention owing to the low toxicity and low cost of copper. However, traditional Ullmann-type couplings suffer from limited substrate scopes and harsh reaction conditions. The introduction of several bidentate ligands, such as amino acids, diamines, 1,3-diketones, and oxalic diamides, over the past two decades has totally changed this situation as these ligands enable the copper-catalyzed coupling of aryl halides and nucleophiles at both low reaction temperatures and catalyst loadings. The reaction scope has also been greatly expanded, rendering this copper-based cross-coupling attractive for both academia and industry. In this Review, we have summarized the latest progress in the development of useful reaction conditions for the coupling of (hetero)aryl halides with different nucleophiles. Additionally, recent advances in copper-catalyzed coupling reactions with aryl boronates and the copper-based trifluoromethylation of aromatic electrophiles will be discussed.

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Novel solid acid catalysts have been prepared from Fudan University (FDU)‐type mesoporous polymers with the Ia d and P6mm mesostructures through a carefully controlled sulfonation procedure. Various techniques have been adopted to characterize throughout their structures, porosity, acidity as well as the information related to the sulfonic acid groups. The sulfonic acid group‐functionalized mesopolymers prove to be efficient heterogeneous catalysts in the reactions such as liquid‐phase Beckmann rearrangement of cyclohexanone oxime and condensation of ethylene glycol with the aldehydes having different molecular sizes.

A class of oxalic diamides are found to be effective ligands for promoting CuI-catalyzed aryl amination with less reactive (hetero)aryl chlorides. The reaction proceeds at 120 °C with K3PO4 as the base in DMSO to afford a wide range of (hetero)aryl amines in good to excellent yields. The bis(N-aryl) substituted oxalamides are superior ligands to N-aryl-N'-alkyl substituted or bis(N-alkyl) substituted oxalamides. Both the electronic nature and the steric property of the aromatic rings in ligands are important for their efficiency.