[ <scp>OH</scp> ‐ <scp>TEMPO</scp> ] ⁺ [ <scp> NO ₃ </scp>

Abstract

The development of sustainable methods for the oxidation of alcohols to aldehydes or ketones remains an important goal in synthesis. In this work, we synthesized a series of nitrate‐bearing oxoammonium salts and demonstrated their efficiency as metal‐free catalysts for the aerobic oxidation of alcohols. These catalysts operate under mild conditions and exhibit a broad substrate scope, efficiently oxidizing both primary and secondary alcohols. The catalytic system performs effectively on a gram scale with industrially relevant substrates, providing a valuable alternative to current protocols. The system operates via a hydride‐transfer mechanism and a self‐sustained NO ₓ ‐mediated redox cycle, with molecular oxygen as the terminal oxidant.