Biocatalytic oxyfunctionalization of unsaturated fatty acids to oxygenated chemicals via hydroxy fatty acids

• Published in: Biotechnology advances Vol. 79; p. 108510
• Main Authors: Oh, Deok-Kun, Lee, Tae-Eui, Lee, Jin, Shin, Kyung-Chul, Park, Jin-Byung
• Format: Journal Article
• Language: English
• Published: England Elsevier Inc 01.03.2025
• Subjects: Biocatalysis; bioplastics; biotechnology; Biotransformation; catalysts; cytochrome P-450; Fatty acid oxygenases; fatty acids; Fatty Acids, Unsaturated - chemistry; Fatty Acids, Unsaturated - metabolism; Hydroxy fatty acids; lactones; leaves; lipoxygenases; Oxidation-Reduction; Oxyfunctionalization; Oxygen - chemistry; Oxygen - metabolism; Oxygenated chemicals; stereoselectivity; Unsaturated fatty acids; Oxyfunctionalization; H(p)OTrE; HPL; HTS; MonoHFA; Fatty acid oxygenases; DiHHME; H(p)FA; DiHFA; E6; UTR; Biotransformation; TriHFA; HSA; H(p)ODE; TriHOME; LDS; MBP; CYP; Hydroxy fatty acids; DiHODE; EH; AI; BVMO; DOX; HOTrEγ; H(p)OME; TriHODE; HODEγ; Unsaturated fatty acids; TriHODEγ; LOX; FAP; DiHOME; POX; Oxygenated chemicals
• ISSN: 0734-9750; 1873-1899; 1873-1899
• DOI: 10.1016/j.biotechadv.2024.108510

The selective oxyfunctionalization of unsaturated fatty acids is difficult in chemical reactions, whereas regio- and stereoselective oxyfunctionalization is often performed in biocatalytic synthesis. Fatty acid oxygenases, including hydratases, lipoxygenases, dioxygenases, diol synthases, cytochrome P450 monooxygenases, peroxygenases, and 12-hydroxylases, are used to convert C16 and C18 unsaturated fatty acids to diverse regio- and stereoselective mono-, di-, and trihydroxy fatty acids via selective oxyfunctionalization. The formed hydroxy fatty acids or hydroperoxy fatty acids are metabolized to industrially important oxygenated chemicals such as lactones, green leaf volatiles, and bioplastic monomers, including ω-hydroxy fatty acids, α,ω-dicarboxylic acids, and fatty alcohols, by biocatalysts. For increased oxyfunctionalization of unsaturated fatty acids, enzyme engineering, functional and balanced expression in recombinant cells, selection of suitable catalyst types, and reaction engineering have been suggested. This review describes biocatalysts involved in the oxyfunctionalization of unsaturated fatty acids and the production of hydroxy fatty acids and oxygenated chemicals. •The active-site structures and mechanisms of fatty acid oxygenases are introduced.•Fatty acid oxygenases convert unsaturated fatty acids into diverse hydroxy fatty acids.•Hydroxy fatty acids are metabolized to oxygenated chemicals by biocatalysts.•The efficient oxyfunctionalization tools of unsaturated fatty acids are suggested.