Direct functionalization of C(sp³)–H bonds allows rapid access to valuable products, starting from simple petrochemicals. However, the chemical transformation of non-activated methylene groups remains challenging for organic synthesis. Here, we report a general electrochemical method for the oxidation of C(sp³)–H and C(sp²)–H bonds, in which cyclic alkanes and (cyclic) olefins are converted into cycloaliphatic ketones as well as aliphatic (di)carboxylic acids. This resource-friendly method is based on nitrate salts in a dual role as anodic mediator and supporting electrolyte, which can be recovered and recycled. Reducing molecular oxygen as a cathodic counter reaction leads to efficient convergent use of both electrode reactions. By avoiding transition metals and chemical oxidizers, this protocol represents a sustainable oxo-functionalization method, leading to a valuable contribution for the sustainable conversion of petrochemical feedstocks into synthetically usable fine chemicals and commodities.

C(sp ³ )–H 键的直接官能化可以从简单的石化产品开始快速获得有价值的产品。然而，非活化亚甲基的化学转化对于有机合成仍然具有挑战性。在这里，我们报告了一种氧化 C(sp ³ )–H 和 C(sp ² )–H 键的通用电化学方法，其中环状烷烃和（环状）烯烃转化为脂环族酮以及脂肪族 (di)羧酸。这种资源友好型方法基于硝酸盐作为阳极介体和支持电解质的双重作用，可以回收和循环利用。减少分子氧作为阴极反反应可以有效地集中使用两个电极反应。通过避免过渡金属和化学氧化剂，该协议代表了一种可持续的氧化功能化方法，为石化原料可持续转化为可合成使用的精细化学品和商品做出了宝贵贡献。