One-procedure synthesis of capsiate from capsaicin by lipase-catalyzed dynamic transacylation

Abstract

Capsiate has a structure similar to capsaicin but no oral pungency. Furthermore, capsiate displayed antioxidant activity and inhibited angiogenesis and vascular permeability, and therefore, showed potential as a medicine and food supplement. Capsaicin is now commercially available, however capsiate is scarcely present in natural foods. We investigated the direct enzymatic conversion of a capsaicinoid to a capsinoid. It was observed that the rate of lipase-catalyzed acylation of vanillyl alcohol with nonanoic acid was faster than that of hydrolysis of N-vanillylnonanamide to vanillyl amide and nonanoic acid in n-hexane at 70°C. As a result, we performed a one-procedure synthesis of capsiate from capsaicin via lipase-catalyzed transacylation.

Practical large-scale production of dihydrocapsiate, a nonpungent capsaicinoid-like substance

“…Acetylated dihydrocapsiate (21) was obtained in good yield without hydrolysis or transesterification of the 4-acetoxy group. Hydroxyphenylalkyl alkanoate (23,24) and ester compounds with an inverse chemical structure compared to CSNs (25,26) were obtained in good yield under similar reaction conditions. [28][29][30][31] Note that an aliphatic ester linkage was selectively constructed in every reaction in the presence of phenol functionality.…”

“…As an example of enzymatic synthesis, the direct conversion of capsaicinoids to CSNs by lipase-catalyzed alcoholysis-type transacylation was reported by Castillo et al and Ishihara et al; however, these methods require considerable amounts of pure capsaicinoids as an acyl donor. 23,24) Another example of condensation of VOH (8) with a fatty acid or a fatty acid methyl ester using the immobilized enzyme Novozym 435 (Novozymes, Denmark), a kind of lipase, in acetone was reported by Kobata et al 25,26) ; however, since the reaction using an enzyme is an equilibrium reaction, the conversion yield of the products was approximately 70-80%, even after long durations of reaction time or by addition of a dehydrating agent such as molecular sieves. Therefore, the equilibrium must shift to the products in some way to improve the yield.…”

Synthesis and Characterization of Phenolic Lipids

“…This is because substrates remove excess water from the immediate vicinity of the enzyme, hence limiting its overall conformational mobility. Ishihara et al [116] studied the efect of temperature on vanillyl alcohol acylation with nonanoic acid to give vanillyl nonanoate in n-hexane solvent medium. The authors found that the optimum temperature for enzymatic acylation was 70°C.…”

“…Generally, its application is oriented toward the speciic detection and potential identiication of chemicals in the presence of other chemicals (in a complex mixture). LC-MS has been used for the structural characterization of lipids and phenolic lipids [10,116].…”

Synthesis of medium-chain length capsinoids from coconut oil catalyzed by Candida rugosa lipases

“…A large body of evidence speaks in favour of enzyme-mediated production of capsinoids. So far, Novozyme 435 has been most extensively used (Ishihara, Kwon, Masuoka, Nakajima, & Hamada, 2010;Kobata et al, 1999). However, the high cost of this catalyst imposes the necessity for alternative approaches (Chang et al, 2014;Zhao, Herbst, Niemeyer, & He, 2015).…”