Arenes are abundantly occurring moleculesof signi?cant interest as versatile starting materials inorganic reactions. Typically, oxidation of arenes yieldsplanar molecules such as phenols and quinones. How-ever, several iron dependent oxygenases can disruptthe aromaticity of arenes through oxidation and intro-duce C(sp3 )?O stereogenic centers, resulting in preciousenantioenriched epoxide or diol products. Emulatingthis enzymatic behavior with synthetic catalysts has metlittle success until now. Herein we describe a catalyticchemo- and enantioselective dearomative epoxidation ofnaphthalenes. The singular chemo- and enantioselectivityfeatures of the reaction critically rely on a manganese cat-alyst that combines electron donating groups and stericdemand on the ligand and activates hydrogen peroxideunder mild conditions and short reaction times. Assistedwith an N-protected amino acid, this catalyst epoxidizesa range of naphthalenes providing chemically versatilediepoxides in moderate to good yields and high levelsof enantioselectivity. Straightforward elaboration givesdiverse access to densely functionalized 3D structurallyrich oxygenated molecules. The reaction constitutes aparadigmatical example of expedient access to stere-ochemically rich, valuable oxygenated molecules fromreadily available feedstocks, enabled by highly reactiveyet selective biologically inspired oxidation catalysts.
It has been recently published open access in Journal of the American Chemical Society:
Najoua Choukairi Afailal, Siu-Chung Chan, and Miquel Costas*
Manganese-Catalyzed Enantioselective Dearomative Epoxidation of Naphthalenes with Aqueous Hydrogen Peroxide
Angew. Chem. Int. Ed. 2025, e202504356
DOI: 10.1002/anie.202504356
Girona, May 8th, 2025
For more info: ges.iqcc@udg.edu