Controlled Heterogeneous Electrocatalytic Oxidation of Carboxylates and Halides for the Synthesis of Novel Chemicals

Abstract The controlled reactivity of the (non)‐Kolbe reaction (for aliphatic acids) or halide oxidation offers a valuable solution for C─C and C─X bond formation. However, traditional Kolbe decarboxylation often suffers from side reactions like homocoupling and overoxidation at high current densities. Here, we introduce P, N‐doped Co₉S₈, named C9S8PN, a versatile adaptive anode catalyst capable of various organo‐electrocatalytic transformations, including magical methylation (alkylation), halogenation, and bromide‐assisted epoxidation. This nano‐material‐based catalyst effectively tames reactive alkyl, chlorine, and bromine radicals, enabling diverse functional group transformations under ambient conditions at an aqueous‐organic interface. Moreover, these reactions proceed at lower potentials, exhibit high chemoselectivity, and demonstrate improved catalyst compatibility compared to traditional methods for selective radical reactions. This work introduces a state‐of‐the‐art approach to suppress homocoupling and selectively promote intramolecular alkylation of decarboxylated radicals using nano‐material‐based heterogeneous surfaces and valorization of readily available electrolytes, leading to valuable transformations. The decarboxylative alkylation of alkenes in the C9S8PN interface arises due to higher double‐layer capacitance in terms of high electrochemical active sites of catalysts.