Synthesis of 9-oxononanoic acid, a precursor for biopolymers.
Polymers based on renewable resources have become increasingly important. The natural functionalization of fats and oils enables an easy access to interesting monomeric building blocks, which in turn transform the derivative biopolymers into high-performance materials. Unfortunately, interesting building blocks of medium-chain length are difficult to obtain by traditional chemical means. Herein, a biotechnological pathway is established that could provide an environmentally suitable and sustainable alternative. A multiple enzyme two-step one-pot process efficiently catalyzed by a coupled 9S-lipoxygenase (St-LOX1, Solanum tuberosum) and 9/13-hydroperoxide lyase (Cm-9/13HPL, Cucumis melo) cascade reaction is proposed as a potential route for the conversion of linoleic acid into 9-oxononanoic acid, which is a precursor for biopolymers. Lipoxygenase catalyzes the insertion of oxygen into linoleic acid through a radical mechanism to give 9S-hydroperoxy-octadecadienoic acid (9S-HPODE) as a cascade intermediate, which is subsequently cleaved by the action of Cm-9/13HPL. This one-pot process afforded a yield of 73 % combined with high selectivity. The best reaction performance was achieved when lipoxygenase and hydroperoxide lyase were applied in a successive rather than a simultaneous manner. Green leaf volatiles, which are desired flavor and fragrance products, are formed as by-products in this reaction cascade. Furthermore, we have investigated the enantioselectivity of 9/13-HPLs, which exhibited a strong preference for 9S-HPODE over 9R-HPODE.
Department of Chemistry, Institute of Technical Biochemistry, Universität Stuttgart, Allmandring 31, 70569 Stuttgart (Germany).
Konrad B
KB
Otte
Marko
M
Kirtz
Bettina M
BM
Nestl
Bernhard
B
Hauer
D055162:Biocatalysis; D001704:Biopolymers / Q000737:chemistry*; D060326:Chemistry Techniques, Synthetic; D028463:Cucumis melo / Q000201:enzymology; D005227:Fatty Acids / Q000138:chemical synthesis* / Q000737:chemistry; D006836:Hydro-Lyases / Q000378:metabolism; D006863:Hydrogen-Ion Concentration; D007651:Keto Acids / Q000138:chemical synthesis* / Q000737:chemistry; D019787:Linoleic Acid / Q000737:chemistry; D008084:Lipoxygenase / Q000378:metabolism; D011198:Solanum tuberosum / Q000201:enzymology; D013237:Stereoisomerism; D013379:Substrate Specificity
D001704:Biopolymers; D005227:Fatty Acids; D007651:Keto Acids; C054931:9-oxononanoic acid; D019787:Linoleic Acid; D008084:Lipoxygenase; C443399:9-hydroperoxide lyase; D006836:Hydro-Lyases
cleavage reactions; enzymes; gas chromatography; lyases; polymers