Single-atom-site (SAS) catalyst, as a highly reactive heterogeneous catalytic system, is one of the effective tools for complex organic synthesis. However, excessive attention on the catalysis and regulation of metal atoms has led to the neglect of the role of supports and ligands. Here, we employed a P-doped porous organic polymer as a support, as well as a ligand in the developed Pd SAS catalysts. The enrichment of the substrates by the pores, ligand action of the support, and high chemoselectivity and anti-agglomeration of SAS catalysts were the most striking features of this SAS catalyst. A highly selective distannylation of terminal alkynes with a new mechanism was achieved by using the multiple properties of SAS catalyst. This catalytic system offers an effective strategy to utilize the enrichment of the substrate by the pores to regulate the reaction mechanism, which opens a new frontier to use pores, ligands, and SASs for synergistic controlling reaction paths.

单原子中心（SAS）催化剂作为一种高反应性的非均相催化系统，是进行复杂有机合成的有效工具之一。然而，对金属原子催化和调节的过度关注导致对载体和配体作用的忽视。在这里，我们在开发的Pd SAS催化剂中采用了P掺杂的多孔有机聚合物作为载体以及配体。孔对基质的富集，载体的配体作用以及SAS催化剂的高化学选择性和抗团聚是该SAS催化剂最显着的特征。利用SAS催化剂的多种性质实现了高选择性的末端炔的脱炔反应。