TY - GEN A1 - Olmedo, Andrés A1 - Aranda, Carmen A1 - Rio, José C. del A1 - Kiebist, Jan A1 - Scheibner, Katrin A1 - Martínez, Angel T. A1 - Gutiérrez, Ana T1 - From Alkanes to Carboxylic Acids: Terminal Oxygenation by a Fungal Peroxygenase T2 - Angewandte Chemie International Edition N2 - A new heme–thiolate peroxidase catalyzes the hydroxylation of n-alkanes at the terminal position—a challenging reaction in organic chemistry—with H2O2 as the only cosubstrate. Besides the primary product, 1-dodecanol, the conversion of dodecane yielded dodecanoic, 12-hydroxydodecanoic, and 1,12-dodecanedioic acids, as identified by GC–MS. Dodecanal could be detected only in trace amounts, and 1,12-dodecanediol was not observed, thus suggesting that dodecanoic acid is the branch point between mono- and diterminal hydroxylation. Simultaneously, oxygenation was observed at other hydrocarbon chain positions (preferentially C2 and C11). Similar results were observed in reactions of tetradecane. The pattern of products formed, together with data on the incorporation of 18O from the cosubstrate H218O2, demonstrate that the enzyme acts as a peroxygenase that is able to catalyze a cascade of mono- and diterminal oxidation reactions of long-chain n-alkanes to give carboxylic acids. KW - Peroxyenase Y1 - 2017 UR - https://opus4.kobv.de/opus4-UBICO/frontdoor/index/index/docId/18606 UR - http://onlinelibrary.wiley.com/doi/10.1002/anie.201605430/abstract SN - 1521-3773 VL - 55 IS - 40 SP - 12248 EP - 12251 ER -