The implementation of heterogeneous catalysts in advanced organic synthesis provides basis for the sustainable and cost-effective preparation of pharmaceuticals, agrochemicals, and other structurally complex molecules. Crucial for such applications is the design of appropriate catalytic materials with high selectivity and functional group compatibility. Although many homogeneous catalysts are well known for this purpose, heterogeneous ones, specifically those based on non-noble metals, are scarce. Here, we present the preparation and wide-ranging applications of a specific atomically dispersed copper catalyst for highly selective carbene insertion reactions of diazo compounds with alcohols, phenols, amines, thiols, and N-heterocycles. The optimal catalyst (Cu-NC/Al₂O₃) contains Al₂O₃-supported copper-based single atoms coordinated with nitrogen species, which can be conveniently prepared by the pyrolysis of Cu-MOF-303. The resulting catalyst allows for the selective formation of C–O, C–N, and C–C bonds in functionalized and structurally diverse molecules (e.g., complex natural products and drugs), including highly sensitive alkynes and azides.

多相催化剂在先进有机合成中的应用为药物、农用化学品和其他结构复杂分子的可持续且经济有效的制备提供了基础。对于此类应用至关重要的是设计具有高选择性和官能团兼容性的适当催化材料。尽管许多均相催化剂用于此目的是众所周知的，但非均相催化剂，特别是基于非贵金属的催化剂却很稀缺。在这里，我们介绍了一种特定的原子分散铜催化剂的制备和广泛应用，用于重氮化合物与醇、酚、胺、硫醇和N-杂环的高选择性卡宾插入反应。最佳催化剂(Cu-NC/Al ₂ O ₃ )含有与氮物种配位的Al ₂ O ₃负载的铜基单原子，可以通过Cu-MOF-303的热解方便地制备。由此产生的催化剂允许在功能化和结构多样的分子（例如复杂的天然产物和药物）中选择性地形成C-O、C-N和C-C键，包括高度敏感的炔烃和叠氮化物。