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

• Published in: Journal of food science 2021-05, Vol.86 (5), p.1714-1725
• Main Authors: Li, Hai‐Mei, Xu, Ting‐Ting, Peng, Qing‐Xia, Chen, Yong‐Sheng, Zhou, Hua, Lu, Yu‐Yun, Yan, Ri‐An
• Format: Article
• Language: English
• Subjects: Acylation; antioxidant activity; Antioxidants; Antiproliferatives; Benzoates; Benzoic acid; benzoic acid ester; Cancer; Conversion; enzymatic acylation; Esters; Flavonoids; Lipid peroxidation; Lipids; Lipophilic; Lipophilicity; Magnetic resonance spectroscopy; Methyl benzoate; NMR; NMR spectroscopy; Nuclear magnetic resonance; Peroxidation; Reaction time; Rhamnose; Rutin; Substrates
• ISSN: 0022-1147; 1750-3841
• DOI: 10.1111/1750-3841.15703

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.