TY - GEN A1 - Kluge, Martin A1 - Ullrich, René A1 - Scheibner, Katrin A1 - Hofrichter, Martin T1 - Stereoselective benzylic hydroxylation of alkylbenzenes and epoxidation of styrene derivatives catalyzed by the peroxygenase of Agrocybe aegerita T2 - Green Chemistry N2 - Here we report on the stereoselective benzylic hydroxylation and C1-C2 epoxidation of alkylbenzenes and styrene derivatives, respectively, by a heme-thiolate peroxygenase (EC 1.11.2.1) from the fungus Agrocybe aegerita. Benzylic hydroxylation led exclusively to the (R)-1-phenylalkanols. For (R)-1-phenylethanol, (R)-1-phenylpropanol and (R)-1-tetralol, the ee reached >99%. For longer chain lengths, the enantiomeric excesses (ee) and total turnover numbers (TTN) decreased while the number of by-products, e.g. 1-phenylketones, increased. Epoxidation of straight chain and cyclic styrene derivatives gave a heterogeneous picture and resulted in moderate to excellent ee values and TTN: e.g., in the case of (1R,2S)-cis-[small beta]-methylstyrene oxide formation, an ee >99% and a TTN of 110 000 was achieved. Hydroxylation and epoxidation were true peroxygenations, which was demonstrated by the incorporation of 18O from H218O2 into the products. The use of fed-batch devices and varying feeding strategies for the substrate and co-substrate turned out to be a suitable approach to optimize peroxygenase catalysis. Y1 - 2014 UR - https://opus4.kobv.de/opus4-UBICO/frontdoor/index/index/docId/11648 UR - http://pubs.rsc.org/en/Content/ArticleLanding/2012/GC/C1GC16173C#!divAbstract SN - 1463-9270 IS - 2 SP - 440 EP - 446 ER -