Aerobic Oxidative Dethioacetalization Catalyzed by an Iron Phthalocyanine Complex

An aerobic oxidative dethioacetalization catalyzed by an iron octacarboxyphthalocyanine complex, which is designed by mimicking enzymatic oxidation, in an aqueous media is developed. The developed method can efficiently convert a broad range of dithioacetals, including those derived from aryl and aliphatic ketones and aldehydes, into the corresponding carbonyl compounds while tolerating various functional groups. This protocol is readily scalable to the gram scale. Mechanistic studies indicate that the iron phthalocyanine complex initiates the reaction by accepting a single electron from the sulfur atom of the dithioacetal, forming a radical cation intermediate. This is followed by unimolecular fragmentation and subsequent degradation of the resulting hemithioacetal to afford the corresponding carbonyl product, along with 1,2‐dithiolane and its oxides.