Enzymatic acylation of rutin with benzoic acid ester and lipophilic, antiradical, and antiproliferative properties of the acylated derivatives

Abstract

Rutin (3′,4′,5,7‐tetrahydroxy‐flavone‐3‐rutinoside) was enzymatically acylated with benzoic acid and its esters (methyl benzoate and vinyl benzoate) using Thermomyces lanuginosus lipase (Lipozyme TLIM). The acylation reaction was optimized by varying the reaction medium, reaction temperature, acyl donor, substrate molar ratio, and reaction time. The highest conversion yield (76%) was obtained in tert‐amyl alcohol (60 °C, 72 hr) using vinyl benzoate (molar ratio of 1:10) as acyl donor. The acylation occurred at the 2′′′‐OH and 4′′′‐OH of the rhamnose unit and the 2′′‐OH position of the glucose moieties. Three novel rutin acylated derivatives (compounds 1–3) were purified and characterized by HR‐MS and 1D and 2D NMR spectroscopy. We found that acylation significantly improved lipophilicity, capacity to inhibit lipid peroxidation, anticancer capacity and substantially maintained the antioxidant activity of rutin. This research provides important insights in the acylation of flavonoids with different glycosyl moieties. Practical Application In this study, three novel rutin derivatives were successfully synthesized and the highest conversion yield (76%) was obtained by reacting the rutin and vinyl benzoate at molar ratio of 1:10 in tert‐amyl alcohol for 72 hr at 60 °C. Introducing a benzoic acid substituent into rutin molecule significantly improved their lipophilicity and inhibition of lipid peroxidation in lipophilic system. Furthermore, this study demonstrated that acylation significantly improved anticancer capacity and substantially maintained the antioxidant activity.

Enzymatic Acylation of Flavonoids from Bamboo Leaves: Improved Lipophilicity and Antioxidant Activity for Oil-Based Foods

“…Cai et al successfully prepared lipid-soluble anthocyanins by grafting cinnamic acids onto anthocyanins from bilberries, which also improved their capacity to inhibit lipid peroxidation . Introducing aromatic acyl groups into rutin significantly improved its lipophilicity, capacity to inhibit lipid peroxidation, and anticancer properties …”

“…17 Introducing aromatic acyl groups into rutin significantly improved its lipophilicity, capacity to inhibit lipid peroxidation, and anticancer properties. 18 Therefore, the goal of the present study was to enzymatically acylate BLFs with vinyl cinnamate using Novozym435. As an important aromatic acid, cinnamic acid is a corrosion-resistant food additive with acyl donors that can induce a strong hydrophobic effect.…”

Direct sulfhydryl ligand derived UiO-66 for the removal of aqueous mercury and its subsequent application as a catalyst for transfer vinylation

“…This reaction affords vinyl benzoates (VBz), which are important derivatives of vinyl ester that are widely used in coatings, inks, adhesives, and biological materials to replace common acrylate class monomers. 27–30 Some mature commercially available vinyl esters can be found in Scheme 1.…”

Flavonoids in Lu’an GuaPian tea as potential inhibitors of TMA‐lyase in acute myocardial infarction

“…Flavonoid aglycones are mainly kaempferol, quercetin, myricetin, and apigenin. The glycosyl group can be glucose, galactose, rhamnose, arabinose, rutinose, and composed of different numbers of glycosyl groups (Godinho et al, 2021; Li et al, 2021). The flavonoids in Lu’an GuaPian tea have a wide range of biological activities and low toxicity and can produce obvious hypoglycemic and myocardial protection (Hua et al, 2018).…”