The development of single-atom catalysts (SACs) with site-specific and tunable catalytic functionalities remains a highly desirable yet challenging goal in catalysis. In this study, we report a SAC featuring anisotropic coordination cavities synthesized via a one-step polymerization of 2,6-diaminopyridine and cyanuric chloride. These cavities provide a robust framework for anchoring isolated Pd single atoms with exceptional stability. The unique broken symmetry of the catalyst's local structure enables precise control over reaction pathways, allowing reactivity to be switched between distinct catalytic outcomes. Specifically, under tailored reaction conditions, the catalyst can either halt at the borylation step or proceed seamlessly to Suzuki coupling in a self-cascade process. Mechanistic studies unveil the pivotal role of Pd single atoms in driving key steps, including oxidative addition, base exchange, and reductive elimination. Furthermore, green metrics demonstrate the process's sustainability, with minimized waste generation and reduced reliance on hazardous reagents in the self-cascade transformation. This work establishes an innovative benchmark in the field of single-atom catalysis: by enabling complex, multistep transformations via strategic activation of multiple functional groups, this catalyst exemplifies the potential of self-cascade processes to revolutionize synthetic chemistry via catalysis engineering.

Department of Chemistry Materials and Chemical Engineering Giulio Natta Politecnico di Milano Piazza Leonardo da Vinci 32 20133 Milano Italy

Department of Energy Science and Engineering Kunsan National University 558 Daehak ro 54150 Gunsan si Republic of Korea

Department of Materials Science University of Milan Bicocca Via Roberto Cozzi 55 20125 Milano Italy

Institute of Physics University of Graz Universitätsplatz 5 8010 Graz Austria

Nanotechnology Centre Centre of Energy and Environmental Technologies VŠB Technical University of Ostrava 17 Listopadu 2172 15 708 00 Ostrava Poruba Czech Republic

Regional Centre of Advanced Technologies and Materials Czech Advanced Technology and Research Institute Palacký University Olomouc Šlechtitelů 241 27 783 71 Olomouc Holice Czech Republic

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