Porous Ligand Creates New Reaction Route: Bifunctional Single-Atom Palladium Catalyst for Selective Distannylation of Terminal Alkynes

Summary 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.