Peroxygenase‐Catalyzed Enantioselective Sulfoxidations

The performances of the unspecific peroxigenase from Agrocybe aegerita ( Aae UPO) in the asymmetric sulfoxidation of substituted aryl alkyl sulfides were here investigated. A small library of differently substituted aryl alkyl sulfoxides was successfully synthesized from the corresponding sulfides in the presence of Aae UPO and H 2 O 2 . All the sulfoxides were obtained as ( R )‐enantiomers, regardless the substitution pattern both on the aromatic ring and the alkyl chain, in up to > 99 % conversion and > 99 % ee . An overview about the biocatalytic entries to chiral sulfoxides is also presented here in form of a comparison between the results obtained with Aae UPO and performances of the chloroperoxidase from Caldariomyces fumago , and three different Baeyer–Villiger monooxygenases. To the best our knowledge, this is the first example of a systematic investigation of the Aae UPO synthetic potential in the asymmetric oxidation of hetero atoms, i.e., the pro‐stereogenic sulfur of sulfides.