Lewis-Acid-Enabled Dual-Site Synergy in Co/Zn Single-Atom Catalysts for Selective N-O Bond Activation of Amides

Abstract

The activation of the N-O bond remains a formidable challenge due to its exceptional stability and resistance to cleavage, which typically requires harsh reaction conditions. In this work, we report a strategically designed cobalt single-atom catalyst (Co-SAC) incorporating Lewis acidic Zn sites that enables the efficient and selective cleavage of N-O bonds in N-OR substituted amides under ambient conditions. The synergistic interaction between atomically dispersed Co centers and adjacent Zn sites facilitated cooperative activation of the N-O bond, thereby lowering the intrinsic energy barrier and promoting facile hydrogen transfer. Comprehensive mechanistic investigations and control experiments revealed that Cat-4's superior catalytic efficiency arises from its optimized dual-site configuration and high surface area. Notably, the catalyst exhibited a broad substrate scope, excellent recyclability over eight cycles, scalability for gram-scale transformations, and the synthesis of bioactive motifs, offering a sustainable platform for the N-O bond activation in N-OR substituted amides.Finally, the green credentials of the catalytic protocols were evaluated using the CHEM21 Green Metrics Toolkit.