Mechanistic insights into the electrochemical oxidation of propargyl alcohols: Molecular oxygen as a hydrogen atom transfer reagent

Abstract We report a sustainable electrochemical method for the synthesis of α,β‐acetylenic ketones (ynones) through the oxidation of propargyl alcohols using molecular oxygen in DMSO, without any additional additives. The reaction proceeds with high site‐selectivity, enabling selective oxidation at the α‐position of the alcohol. Mechanistic investigations indicate a hydrogen atom transfer (HAT) pathway in which molecular oxygen functions as the HAT reagent. Key intermediates were identified, and the proposed mechanism is supported by electrochemical studies and DFT calculations, providing valuable insight into this oxygen‐mediated oxidation process.