Modular Synchronous Synthesis of Amides and α‐Ketoamides Realized by Matching Electrolysis‐Paired Tandems

Abstract

Abstract Feasible electrolysis‐paired tandem synthesis represents an elaborately organized and high‐efficiency strategy balancing energy consumption and value‐added synthesis. Herein, we developed an exotic electrolysis‐paired tandem synthesis system driven by a metalloenzyme‐like bifunctional single‐molecular heterostructure catalyst (MimNiPc/CNT), which enables the modular synchronous synthesis of amides and α‐ketoamides through cathodic CO‐relayed aminocarbonylation and anodic iodine (I 2 )‐mediated keto‐amidation tandem reactions, respectively. Notably, the established MimNiPc/CNT is not only effective for parallel electrolysis‐paired tandem reactions with various substrates but also adaptable for both divergent and sequential electrolysis‐paired tandem reactions, producing value‐added amide and α‐ketoamide compounds with isolated yields up to ∼90%. Detailed isotope labeling and mass spectrometry tracking experiments meticulously unveiled the reaction mechanisms, the processes at both electrodes can be refined into sequential electrocatalysis and chemocatalysis steps. Our work also demonstrates the flexibility and scalability of this “two birds with one stone” synthetic protocol, providing an experimental reference for precise synthesis.