Low‐Impact Synthesis of γ‐Lactones through Photoinduced Baeyer‐Villiger Oxidation of Cyclic Ketones

• Published in: European journal of organic chemistry Vol. 27; no. 21
• Main Authors: Cabua, Maria Chiara, Velichko, Viktoria, Pilia, Luca, Moi, Davide, Secci, Francesco
• Format: Journal Article
• Language: English
• Published: WEINHEIM Wiley 03.06.2024; Wiley Subscription Services, Inc
• Subjects: Acetonitrile; Anthraquinones; Catalysts; Chemistry; Chemistry, Organic; Cyclobutanone; Ketones; Lactones; Oxidation; Photo-oxidation; Photocatalysis; Physical Sciences; Room temperature; Science & Technology; γ-Lactone; gamma-Lactone; ELECTRON; Photocatalysis; Cyclobutanone; DESYMMETRIZATION; ALCOHOLS; OXYGEN; Photo-oxidation; Anthraquinones; KINETIC RESOLUTION; PLATINUM(II); PHOTOCHEMISTRY; LACTONIZATION; PHOTOOXYGENATION; EFFICIENT
• ISSN: 1434-193X; 1099-0690
• DOI: 10.1002/ejoc.202400226

A photocatalyzed oxidation of functionalized cyclobutanones to access γ‐lactones has been performed in acetonitrile at room temperature, using anthraquinone derivatives as catalysts in the presence of TFA. The best reaction results were obtained by using 3 mol % of 9,10‐anthraquinone as a catalyst under 370 nm irradiation in an O2 environment. The scope and the limitations of this reaction have been investigated using both 2‐ and 3‐substituted cyclobutanones, as well as enantiopure ketones, to obtain full preservation of their stereochemical identity after the oxidation. The process furnishes in most cases the desired compounds with high purity after catalyst removal by simple filtration, and reducing the production of solvents waste. A photocatalyzed oxidation of functionalized cyclobutanones to access γ‐lactones has been performed in acetonitrile at room temperature, using 9,10‐anthraquinone as catalysts in the presence of TFA. The process furnish good to excellent yields of the desired compounds in 4–16 h reaction and after simple filtration of the recyclable catalyst.