- Influence of the ionic liquid cosolvent on glucosylation reactions catalyzed by b-glycosidase for production of salidroside
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The enzymatic synthesis of salidroside catalyzed by b-glycosidase from Malus pumila seed meal has been successfully carried out in ionic liquids-containing systems for the first time. The optimum conditions were screened out and the best yield of 24.9 % w
- Bi, Yanhong,Zhu, Chun,Wang, Zhaoyu,Jia, Jianbo
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- A Sustainable One-Pot, Two-Enzyme Synthesis of Naturally Occurring Arylalkyl Glucosides
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A sustainable, convenient, scalable, one-pot, two-enzyme method for the glucosylation of arylalkyl alcohols was developed. The reaction scheme is based on a transrutinosylation catalyzed by a rutinosidase from A. niger using the cheap commercially available natural flavonoid rutin as glycosyl donor, followed by selective “trimming” of the rutinoside unit catalyzed by a rhamnosidase from A. terreus. The process was validated with the syntheses of several natural bioactive glucosides, which could be isolated in up to 75 % yield without silica-gel chromatography.
- Bassanini, Ivan,Krejzová, Jana,Panzeri, Walter,Monti, Daniela,K?en, Vladimir,Riva, Sergio
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- Rapid biosynthesis of phenolic glycosides and their derivatives from biomass-derived hydroxycinnamates
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Biomass-derived hydroxycinnamates (mainly includingp-coumaric acid and ferulic acid), which are natural sources of aromatic compounds, are highly underutilized resources. There is a need to upgrade them to make them economically feasible. Value-added phenolic glycosides and their derivatives, both belonging to a class of plant aromatic natural products, are widely used in the nutraceutical, pharmaceutical, and cosmetic industries. However, their complex aromatic structures make their efficient biosynthesis a challenging process. To overcome this issue, we created three novel synthetic cascades for the biosynthesis of phenolic glycosides (gastrodin, arbutin, and salidroside) and their derivatives (hydroquinone, tyrosol, hydroxytyrosol, and homovanillyl alcohol) fromp-coumaric acid and ferulic acid. Moreover, because the biomass-derived hydroxycinnamates directly provided aromatic units, the cascades enabled efficient biosynthesis. We achieved substantially high production rates (up to or above 100-fold enhancement) relative to the glucose-based biosynthesis. Given the ubiquity of the aromatic structure in natural products, the use of biomass-derived aromatics should facilitate the rapid biosynthesis of numerous aromatic natural products.
- Zhao, Mingtao,Hong, Xulin,Abdullah,Yao, Ruilian,Xiao, Yi
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- Use of apple seed meal as a new source of β-glucosidase for enzymatic glucosylation of 4-substituted benzyl alcohols and tyrosol in monophasic aqueous-dioxane medium
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A facile method for enzymatic glycosylation of 4-substituted benzyl alcohols and tyrosol with glucose in a monophasic aqueous-dioxane medium was reported, using a crude meal of apple seed as a new catalyst. The corresponding β-D-glucosides were synthesized in moderate yields (13.1-23.1%), among which the salidroside was obtained in 15.8% yield.
- Tong, Ai Min,Lu, Wen Ya,Xu, Jian He,Lin, Guo Qiang
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- Aryl β-d-glucosides from Carica papaya fruit
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Benzyl β-d-glucoside, 2-phenylethyl β-d-glucoside, 4-hydroxyphenyl-2-ethyl β-d-glucoside and four isomeric malonated benzyl β-d.
- Schwab, Wilfried,Schreier, Peter
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- Ionic Liquid Effects on the Activity of β-Glycosidase for the Synthesis of Salidroside in Co-solvent Systems
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The preparation of salidroside was successfully carried out in fourteen ionic liquids (ILs)-containing systems using β-glycosidase from black plum seeds for the first time. The optimum conditions were determined for C6MIm·BF4, pH, phosphate buffer content, and molar ratio of tyrosol to D-glucose to be 1% (v/v), 5.9, 20% (v/v), and 8:1, under which the initial reaction rate and yield were 3.3 mmol/(L·h) and 24.5%, respectively. Moreover, the effects of 1-alkylimidazolium-based ILs possessing different alkyl chain lengths from C2 to C10 and a variety of anions including BF4-, PF6-, Cl-, Br-, and I- on enzyme activity in co-solvent systems were investigated. The results indicate that the optimal chain length of the alkyl substituent on the imidazolium ring of the cation was C6.
- Bi, Yanhong,Wang, Zhaoyu,Mao, Yanyong,Zheng, Shangyong,Zhang, Haijiang,Shi, Hao
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- PHENOLIC GLUCOSIDES FROM PRUNUS GRAYANA
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A new bitter phenylpropanoid glucoside, 2-(4-hydroxyphenyl)-ethyl-(6-O-caffeoyl)-β-D-glucopyranoside and a new bitter tannin-related compound, 3,4,5-trimethoxybenzoyl-β-D-glucopyranoside, have been isolated together with known compounds, 2-(3,4-dihydroxyphyenyl)-ethyl-(6-O-caffeoyl)-β-D-glucopyranoside,2-(3,4-dihydroxyphenyl)-ethyl-β-D-glucopyranoside and 6-O-caffeoyl-D-glucopyranose, from the bark of Prunus grayana.The structures of these compounds have been established on the basis of spectroscopic studies and chemical evidence. Key Word Index--Prunus grayana; Rosaceae; phenylpropanoid glucosides; tannin-related compound; caffeic acid esters; 3,4,5-trimethoxybenzoic acid ester.
- Shimomura, Hiroko,Sashida, Yutaka,Adachi, Tokuo
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- Chemical synthesis method of salidroside
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The invention discloses a synthesis method of salidroside, wherein a phenolic hydroxyl group of a tyrosol is protected by a benzoyl group to carry out an acylation reaction, and beta-D-pent-acetyl glucose is used as a raw material and a glycosylation reaction is performed under the catalyst of zinc chloride and deprotection is performed in a methanol system of sodium methoxide. The synthesis method optimizes the synthesis route of salidroside, shortens the reaction steps, and improves the yield and the reaction conditions are mild, the operation is simple and easy, and the production cost is greatly reduced.
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Paragraph 0019; 0024-0025; 0026; 0031-0032; 0033; 0036-0037
(2019/03/28)
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- Preparation of salidroside with n-butyl β-D-glucoside as the glycone donor via a two-step enzymatic synthesis catalyzed by immobilized β-glucosidase from bitter almonds
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β-Glucosidase from bitter almonds was immobilized on epoxy group-functionalized beads for catalyzing salidroside synthesis in a two-step process with n-butyl-β-D-glucoside (BG) as the glucosyl donor. The formation of salidroside ((0.59 ± 0.02) M) at a yield of 39.04%±1.25% was accomplished in 8 h by the transglucosylation of immobilized β-glucosidase at pH?8.0 and 50 °C when the ratio of BG to tyrosol was 1:2 (mol/mol). A study on the influence of different glycosyl acceptors demonstrated that the yield of the glucosylation reaction of phenylmethanol and cyclohexanol was higher than that of either phenol or cyclohexanol. This may account for the selectivity of the immobilized enzyme towards the alcoholic hydroxyl group of tyrosol in the salidroside synthesis reaction. A study on the synthesis of BG via the reverse hydrolysis of immobilized β-glucosidase showed that a yield of 78.04%±2.2% BG can be obtained with a product concentration of (0.23 ± 0.015) M.
- Wang, Feng,Huang, Dengfa,Ma, Yong,Zhang, Fuming,Linhardt, Robert J.
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p. 246 - 260
(2019/02/03)
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- Method for synthesizing salidroside by using [Rmim][OSO2OR]-Lewis acid ionic liquid system
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The invention belongs to the technical field of catalytic synthesis and particularly relates to a method for synthesizing salidroside by using a [Rmim][OSO2OR]-Lewis acid ionic liquid system. According to the method, the salidroside compound is synthesized by using ionic liquid [Rmim][OSO2OR]. The synthesis of the ionic liquid provided by the invention needs only a one-step reaction, and atoms ofraw materials in a synthetic reaction of the ionic liquid are utilized by 100%, and thus, the reaction is an atomic-economical-efficiency reaction with simple and convenient operation. The method provided by the invention is environmentally friendly and is mild in reaction conditions and simple in aftertreatment, the problems such as environmental pollution caused by tedious synthesis of the ionicliquid used during the existing O-Glycosylation of a glycosyl trichloroacetimidate donor by using an ionic liquid system, thermal energy consumption, atom waste and a non-atomic-economical-efficiencyreaction are solved, and meanwhile, the problems such as environmental pollution and tedious aftertreatment caused by the existing salidroside drug chemical-synthesis in organic solvents are solved.
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- Preparation method of natural product salidroside
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The invention provides a new method for total synthesis preparation of salidroside. The method is characterized by comprising the following steps: reacting glucose pentaacetate (I) with 4-acetoxy phenethyl alcohol (II) in an organic solvent under the catalysis of a catalyst MXbLc to obtain 2-(4-acetoxyphenyl)-ethyl-(2,3,4,6-O-tetraacetyl)-beta-D-glucopyranoside (III); and performing deacetylation protection on the 2-(4-acetoxyphenyl)-ethyl-(2,3,4,6-O-tetraacetyl)-beta-D-glucopyranoside (III) to obtain salidroside.
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- A suitable for industrial production process for the separation of chemical synthesis salidroside
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The invention discloses a separation method suitable for chemical synthesis of salidroside for industrial production. The method comprises the following steps: carrying out a reaction on Beta-D-pent-acetyl glucose and hydroxyphenethyl alcohol under the catalytic action of a lewis acid; and carrying out deacetylation on a generated tetraacetyl salidroside product so as to prepare the salidroside. Thus, the salidroside product is synthesized in a separating manner via an extraction and recrystallization method while a simple and convenient synthesis method is adopted at the same time. Compared with the traditional chemical synthesis process, the method disclosed by the invention is low in cost, high in yield, short in reaction time, simple and simple, convenient and environmentally friendly in synthesis process, thereby being suitable for industrial production, and the raw materials are easily available.
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Page/Page column 0024; 0027-0030; 0033-0035; 0038-0040; 0043; 0044
(2019/02/04)
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- A method for synthesizing of salidroside and wherein the intermediate compound (by machine translation)
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The invention discloses a method for synthesizing of salidroside and intermediate compound thereof. The method comprises the following steps : (1) the protection of the hydroxyl group protected with an acyl phenethylol glucose of the Lewis acid in an organic solvent under the catalysis of 1 reaction, intermediate results in the type shown in (IV) ; (2) shown in the formula (IV) in the intermediates C1-C4 in alkanol, in the presence of alkali acyl protecting group removal, drying, to obtain the I; formula (III) and (IV) the definition of the substituent in the specification. The synthetic method of this invention has the advantages of simple operation, mild conditions, the advantages of high yield and the easy industrialization. (by machine translation)
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Paragraph 0065; 0066
(2016/10/07)
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- A selective and mild glycosylation method of natural phenolic alcohols
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Several bioactive natural p-hydroxyphenylalkyl β-D-glucopyranosides, such as vanillyl β-D-glucopyranoside, salidroside and isoconiferin, and their glycosyl analogues were prepared by a simple reaction sequence. The highly efficient synthetic approach was achieved by utilizing acetylated glycosyl bromides as well as aromatic moieties and mild glycosylation promoters. The aglycones, p-O-acetylated arylalkyl alcohols, were prepared by the reduction of the corresponding acetylated aldehydes or acids. Various stereoselective 1,2-trans-O-glycosylation methods were studied, including the DDQ-iodine or ZnO-ZnCl2 catalyst combination. Among them, ZnO-iodine has been identified as a new glycosylation promoter and successfully applied to the stereoselective glycoside synthesis. The final products were obtained by conventional Zemplén deacetylation.
- Mastihubová, Mária,Poláková, Monika
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p. 524 - 530
(2016/04/08)
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- Using ionic liquid cosolvents to improve enzymatic synthesis of arylalkyl β-d-glucopyranosides
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Enzymatic synthesis of various arylalkyl β-d-glucopyranosides catalyzed by prune (Prunus domestica) seed meal via reverse hydrolysis in the mixture of organic solvent, ionic liquid (IL) and phosphate buffer was described. Among four hydrophilic organic solvents tested, ethylene glycol diacetate (EGDA) was found to be the most suitable for enzymatic synthesis of salidroside, a bioactive compound of commercial interest, from d-glucose and tyrosol. The effects of the nature of ionic liquids and their contents on the enzymatic glucosylation were studied. The addition of a suitable amount of ILs including denaturing ones was favorable to shift the reaction equilibrium toward the synthesis, thus improving the yields. Among the examined ILs, the novel IL [BMIm]I proved to be the best. And this IL was applied as the solvent in biocatalysis for the first time. The yields were found to be enhanced between 0.2-fold and 0.5-fold after the addition of 10% (v/v) [BMIm]I. In 10% (v/v) [BMIm]I-containing system, the desired arylalkyl β-d-glucopyranosides were synthesized with 15-28% yields, among which salidroside was obtained with a yield of 22%. .
- Yang, Rong-Ling,Li, Ning,Zong, Min-Hua
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experimental part
p. 24 - 28
(2012/05/19)
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- Development of a kilogram-scale synthesis of salidroside and its analogs
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An efficient, safe, and viable process has been developed for large-scale preparation of salidroside, a natural product. The process consists of two chemical steps, which produce the salidroside on a multikilogram scale with 72% overall yield and >98% purity.A series of novel salidroside analogs were prepared according to the same method. Taylor & Francis Group, LLC.
- Shi, Tianyao,Chen, Hui,Jing, Linlin,Liu, Xueying,Sun, Xiaoli,Jiang, Ru
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experimental part
p. 2594 - 2600
(2011/08/07)
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- Terpenoids and phenethyl glucosides from Hyssopus cuspidatus (Labiatae)
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Monoterpenoids (3 and 4), sesquiterpenoid (2), diterpenoid (1) and four phenethyl glucosides (5-8), together with fourteen known compounds, were isolated from the whole herb of Hyssopus cuspidatus. Their structures were determined by spectroscopic means.
- Furukawa, Megumi,Makino, Mitsuko,Ohkoshi, Emika,Uchiyama, Taketo,Fujimoto, Yasuo
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experimental part
p. 2244 - 2252
(2012/07/03)
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- Chemical constituents from the fruits of Ligustrum lucidum
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One new δ-valerolactone (1) and one new natural phenolic glycoside 2, together with four known compounds 3-6, were isolated from the fruits of Ligustrum lucidum. Their structures were elucidated on the basis of spectral data. The chemical transformation from 2 to 3 was observed. The immunomodulatory activities of the compounds were also evaluated.
- Liu, Xin,Wang, Chang-Yun,Shao, Chang-Lun,Fang, Yu-Chun,Wei, Yu-Xi,Zheng, Cai-Juan,Sun, Ling-Ling,Guan, Hua-Shi
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experimental part
p. 701 - 703
(2011/03/19)
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- Synthesis, biological activity of salidroside and its analogues
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Salidroside is a phenylpropanoid glycoside isolated from Rhodiola rosea L., a traditional Chinese medicinal plant, and has displayed a broad spectrum of pharmacological properties. In this paper, about 18 novel salidroside analogues were prepared through Koenigs-Knorr method, the effects of these compounds over PC12 was assessed with the 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) method. The novel compounds differ in the substituents attached to the benzene ring or in the glycosyl donor. According to the data, compounds (3,5-dimethoxyphenyl)methyl β-D-glucopyranoside and (3,5-dimethoxyphenyl) methyl β-D-galactopyranoside with methoxy group at 3 and 5-positions of the benzene ring were the most viability at concentration of 300 μmol/l and 60 μmol/l, respectively.
- Guo, Yibing,Zhao, Yahong,Zheng, Cheng,Meng, Ying,Yang, Yumin
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experimental part
p. 1627 - 1629
(2011/02/24)
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- Chemoenzymatic syntheses of naturally occurring β-glucosides
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Enzymatic glycosidation of the various kinds of primary alcohols 5, 7, 9, 11, 13 and 15 and 4-nitrophenyl-β-D-glucopyranoside 4 using β- glucosidase from almonds gave stereoselectively β-D-glucosides 6, 8, 10, 12, 14 and 16 including the naturally occurring β-glucosides in moderate yield. Among them, the β-glucosides 6, 8 and 10 were converted to the cyanoglycosides, rhodiocyanoside A 20a, osmaronin 24a and sutherlandin 29, respectively.
- Akita, Hiroyuki,Kurashima, Katsumi,Nakamura, Takuya,Kato, Keisuke
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p. 2429 - 2439
(2007/10/03)
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- Synthesis of 13C-labeled possible intermediates in the biosynthesis of phenylethanoid derivatives, cornoside and rengyosides
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In order to clarify the biosynthetic pathway of C6-C2 unit compounds containing salidroside, cornoside, and rengyosides A and B in oleaceous plants, 13C-labeled putative precursors, 4-hydroxyphenylethanol, salidroside and cornoside, were prepared.
- Kuwajima, Hiroshi,Takai, Yoshitaka,Takaishi, Kiyokazu,Inoue, Kenichiro
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p. 581 - 586
(2007/10/03)
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- BIOGENESIS-LIKE TRANSFORMATION OF SALIDROSIDE TO RENGYOL AND ITS RELATED CYCLOHEXYLETANOIDS OF FORSYTHIA SUSPENSA
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Photooxygenation of salidroside (8) in methanol in presence of Rose Bengal afforded cornoside (9), which, on high pressure hydrogenation with 5percent palladium on activated carbon, yielded rengyoside B (6).Reduction of 6 with sodium borohydride gave rengyoside A(5) stereoselectively.By enzymatic hydrolysis, 9, 6 and 5 furnished rengyolone (4), rengyoxide (3) and rengyol (1), respectively. Similerly, p-hydroxyphenylethanol (10), the aglycone part of salidroside (8), was oxygenated photochemically to a dienone alcohol, which cyclized spontaneously to rengyolone (4).Hallerone (17) was obtained by the photooxygenation of p-hydroxyphenylethyl acetate (10b).Thus the plausible biosynthetic routes from salidroside (8) to rengyol (1) and the related natural cyclohexylethanoids were simulated chemically.
- Endo, Katsuya,Seya, Kazuhiko,Hikino, Hiroshi
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p. 3673 - 3682
(2007/10/02)
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