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Biocatalytic Oxidative Cascade for the Conversion of Fatty Acids into α‐Ketoacids via Internal H 2 O 2 Recycling
Author(s) -
Gandomkar Somayyeh,
Dennig Alexander,
Dordic Andela,
Hammerer Lucas,
Pickl Mathias,
Haas Thomas,
Hall Mélanie,
Faber Kurt
Publication year - 2018
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201710227
Subject(s) - chemistry , hydroxylation , monooxygenase , biocatalysis , oxidative phosphorylation , cascade , catalysis , yield (engineering) , organic chemistry , cascade reaction , regioselectivity , fatty acid , combinatorial chemistry , enzyme , biochemistry , reaction mechanism , cytochrome p450 , chromatography , materials science , metallurgy
The functionalization of bio‐based chemicals is essential to allow valorization of natural carbon sources. An atom‐efficient biocatalytic oxidative cascade was developed for the conversion of saturated fatty acids to α‐ketoacids. Employment of P450 monooxygenase in the peroxygenase mode for regioselective α‐hydroxylation of fatty acids combined with enantioselective oxidation by α‐hydroxyacid oxidase(s) resulted in internal recycling of the oxidant H 2 O 2 , thus minimizing degradation of ketoacid product and maximizing biocatalyst lifetime. The O 2 ‐dependent cascade relies on catalytic amounts of H 2 O 2 and releases water as sole by‐product. Octanoic acid was converted under mild conditions in aqueous buffer to 2‐oxooctanoic acid in a simultaneous one‐pot two‐step cascade in up to >99 % conversion without accumulation of hydroxyacid intermediate. Scale‐up allowed isolation of final product in 91 % yield and the cascade was applied to fatty acids of various chain lengths (C6:0 to C10:0).