Biocatalytic Aromaticity-Breaking Epoxidation of Naphthalene and Nucleophilic Ring-Opening Reactions

Aromatic hydroxylation reactions catalyzed by heme-thiolate enzymes proceed via an epoxide intermediate. These aromatic epoxides could be valuable building blocks for organic synthesis giving access to a range of chiral trans-disubstituted cyclohexadiene synthons. Here, we show that naphthalene generated fungal peroxygenases can subjected nucleophilic ring opening, yielding non-racemic derivates, which in turn used further chemical transformations. This approach may represent promising shortcut the natural products and APIs.