Air-Stable Copper(I) Single-Atom Site Catalysts for Highly Selective Borylative Allyl–Allyl Cross-Coupling

Borylative allyl–allyl coupling reactions of allenes are an efficient strategy for constructing 1,5-diene skeletons. Nevertheless, this reaction poses challenges in achieving precise chemical selectivity and stereochemical control. We designed an air-stable copper(I) single-atom site catalyst (SASC), Cu@POL-bpy, with high regioselectivity for borylative allyl–allyl coupling of aryl-allenes. This breakthrough resulted from thorough investigations into structure–performance relationships, highlighting the importance of the hierarchical porosity and metal–support interactions of the catalyst. The catalytic system had a surface area of 961 m2/g and attained a turnover number (TON) of 2607.4, representing almost a 150-fold improvement over previous catalytic systems. This study highlights the promise of SASCs in organic synthesis and provides valuable insights and tools for advancing synthetic chemistry.