Catechins and Derivatives Synthesis and Pharmacological Activity Research Progress

Abstract

Abstract: Catechins not could anti-tumor, anti-oxidation, anti-bacterial, anti-virus but protect heart,brain and other pharmacological effects. Catechins mainly exist in tea plant in nature, the biosynthesis pathways has been basically cleard. On the other hand, researchers also working on chemical synthesis to acquire more quantity of catechins. Its polyhydroxy structure provides bioactivity while also making catechins unstable under neutral, alkaline and heating conditions. Catechins which ingested by human body will soon be methylated or glycosylated by biotic enzyme, resulting in lower bioavailability and limit its clinical application severely . The study found that the introduction of other groups to the catechins structure can effectively improve the stability and bioavailability, and enhance the pharmacological effects of catechins specifically, in addition, different groups could bring different effects. Among them, methyled catechin is well in allergy and reversal of tumor cell resistance, and full methylation get strongest effection. glycosylated catechins have good solubleness and prevent browning effectively. and acylated catechins’ property of anti-oxidant and anti-tumor activity also significantly enhanced due to fat-soluble significantly. The effect of substituting at different locations is also not the same, substituted at C4′ influence effects mostly. In this paper, catechin biosynthesis and chemical synthesis pathway are introduced in detail, the different derivative methods of catechins are reviewed and their pharmacological effects are described briefly. Catechins derivatives research has been matured, but there is still no drugs applicated to clinic. In the future, we could combine the different derivative methods, focus on substitute at B ring, and work for practical medical value.

Key words: biosynthesis, chemical synthesis, structural modification, pharmacological effects, research prospect

CLC Number:

O629.9

Chang-qi Lu. Catechins and Derivatives Synthesis and Pharmacological Activity Research Progress[J]. FOOD SCIENCE, 0, (): 0-0.

References

[1]宛晓春.茶叶生物化学[Z]. 3. 北京: 中国农业出版社, 20039-15.
[2]Nakanishi T, Mukai K, Yumoto H, et al.Anti-inflammatory effect of catechin on cultured human dental pulp cells affected by bacteria-derived factors[J].Eur J Oral Sci, 2010, 118(2):145-150
[3]Nance C L, Siwak E B, Shearer W T.Preclinical development of the green tea catechin,epigallocatechin gallate,as an HIV-1 therapy[J].Journal of Allergy and Clinical Immunology, 2009, 123(2):459-465
[4]Frei B, Higdon J.Antioxidant Activity of Tea Polyphenols In Vivo: Evidence from Animal Studies[J].Journal of Nutrition, 2003, 133(10):3275-3284
[5]Kumar D, Harshavardhan S J, Chirumarry S, et al.Design,Synthesis in vitro anticancer activity and docking studies of (-)-catechin derivatives[J].Bulletin of The Korean Chemical Society, 2015, 36(2):564-570
[6]Manikandan R, Beulaja M, Arulvasu C, et al.Synergistic anticancer activity of curcumin and catechin: An in vitro study using human cancer cell lines[J].Microscopy Research and Technique, 2012, 75(2):112-116
[7]霍远涛, 王辉.表没食子酸儿茶素没食子酸酯的抗癌机制研究[J]. 实用医技杂志, 2016(03):253-255.[J].实用医技杂志, 2016, 未知(03):253-255
[8]Rathore K, Choudhary S, Odoi A, et al.Green tea catechin intervention of reactive oxygen species-mediated ERK pathway activation and chronically induced breast cell carcinogenesis[J].Carcinogenesis, 2011, 33(1):174-183
[9]刘珊丽, 刘宗文, 卢沛琦, 等.儿茶素对大鼠脑缺血/再灌注损伤的保护作用及机制[J].中国药理学通报, 2010, :255-257
[10]徐先祥.儿茶素的药理作用研究综述[J].郑州轻工业学院学报(自然科学版), 2012, :60-64
[11]于莎莎, 丁阳平, 罗赛, 等.儿茶素衍生物合成及药理作用研究进展[J]. 食品科学, 2012(17):318-326.
[12]柳敏, 饶国武, 华允芬.EGCG衍生物合成及药理活性研究进展[J]. 茶叶科学, 2016(02):119-130.
[13]夏涛, 高丽萍.类黄酮及茶儿茶素生物合成途径及其调控研究进展[J]. 中国农业科学, 2009(08).
[14]夏涛, 高丽萍, 刘亚军, 等.茶树酯型儿茶素生物合成及水解途径研究进展[J]. 中国农业科学, 2013(11):2307-2320.
[15]宛晓春, 夏涛, 张正竹, 等.茶树次生代谢: 茶树次生代谢[Z]. 夏涛. 北京: 科学出版社, 201539-59.
[16]Meada H, Dudareva N.The Shikimate Pathway and Aromatic Amino Acid Biosynthesis in Plants[J]. 2012, 23(1):73-105.
[17]Stafford H A, Lester H H.Flavan-3-ol Biosynthesis The Conversion of (+)-Dihydromyricetin to Its Flavan-3,4-Diol (Leucodelphinidin) and to (+)-Gallocatechin by reductases extracted from tissue cultures of Ginkgo biloba and Pseudotsuga menziesii[J].Plant Physiology, 1985, 4(78):791-794
[18]Xie D.Role of Anthocyanidin Reductase,Encoded by BANYULS in Plant Flavonoid Biosynthesis[J].Science, 2003, 5605(299):396-399
[19]Niemetz R, Gross G G.Enzymology of gallotannin and ellagitannin biosynthesis[J].Phytochemistry, 2005, 66(17):2001-2011
[20]Gross G G.From lignins to tannins: Forty years of enzyme studies on the biosynthesis of phenolic compounds[J].Phytochemistry, 2008, 69(18):3018-3031
[21]Liu Y, Gao L, Liu L, et al.Purification and Characterization of a Novel Galloyltransferase Involved in Catechin Galloylation in the Tea Plant (Camellia sinensis)[J].Journal of Biological Chemistry, 2012, 287(53):44406-44417
[22]Zhong K, Shao Z, Hong F.Enzymatic Production of Epigallocatechin by Using an Epigallocatechin Gallate Hydrolase Induced from Aspergillus oryzae[J].Biotechnology Progress, 2008, 24(3):583-587
[23]Zhong K, Zhao S, J?nsson L J, et al.Enzymatic conversion of epigallocatechin gallate to epigallocatechin with an inducible hydrolase fromAspergillus niger[J].Biocatalysis and Biotransformation, 2009, 26(4):306-312
[24]Tanaka H, Chino A, Takahashi T.Reagent-controlled stereoselective synthesis of (+-)-gallo- and (+-)-epigallo-catechin gallates[J].TETRAHEDRON LETTERS, 2012, 53(20):2493-2495
[25]Asakawa T, Hamashima Y, Kan T.Chemical Synthesis of Tea Polyphenols and Related Compounds[J]. Current Pharmaceutical Design, 2013, 19:6207-6217.
[26]Oyama K, Yoshida K, Kondo T.Recent Progress in the Synthesis of Flavonoids: From Monomers to Supra-Complex Molecules[J].Current Organic Chemistry, 2011, 15(15):2567-2607
[27]Sundeep D, Dinesh M, Santosh R K, et al.Novel Approach for Synthesis of Catechins: 2014.07.31.
[28]Dengming H, Lihuijing, Yanchao W.Synthesis method of procyanidine compound Catechin: 2016.06.11.
[29]曾晓雄, 高远, 张鑫, et al.Method for preparing tea polyphenol rich in methylatedcatechin: 2011.06.08.
[30]Kida K, Suzuki M, Matsumoto N, et al.Identification of biliary metabolites of (-)-epigallocatechin gallate in rats[J].Journal of Agricultural and Food Chemistry, 2000, 48(9):4151-4155
[31]Meng X F, Lee M J, Li C, et al.Formation and identification of 4 '-O-methyl-(-)-epigallocatechin in humans[J].Drug Metabolism and Disposition, 2001, 29(6):789-793
[32]Lu H, Meng X F, Yang C S.Enzymology of methylation of tea catechins and inhibition of catechol-O-methyltransferase by (-)-epigallocatechin gallate[J].Drug Metabolism Disposition, 2003, 31(5):572-579
[33]Okushio K, Suzuki M, Matsumoto N, et al.Methylation of tea catechins by rat liver homogenates[J].Bioscience Biothchnology and Biochemistry, 1999, 63(2):430-432
[34]吕海鹏, 费冬梅, 张悦, 等.EGCG-O-甲基转移酶(EOMT)催化EGCG形成的EGCG甲基化衍生物分析[J]. 茶叶科学, 2012(02):100-106.
[35]吕海鹏, 费冬梅, 张悦, 等.EGCG甲基化衍生物酶促合成的反应条件研究[J]. 茶叶科学, 2012(05):441-447.
[36]廖作庄.表没食子儿茶素没食子酸酯衍生物的合成与逆转人肝癌细胞MDR作用的研究[D]. 广西医科大学, 2011.
[37]李福星.甲基化儿茶素衍生物的设计合成及抗肿瘤多药耐药活性研究[D]. 中国海洋大学, 2015.
[38]Meaeda-Yamamoto M, Ema K, Shibuichi I.In vitro and in vivo anti-allergic effects of 'benifuuki' green tea containing O-methylated catechin and ginger extract enhancement[J].Cytotechnology, 2007, 55(2-3):135-142
[39]伍妍俊, 汪小钢, 宛晓春.甲基化EGCG的研究现状及展望[J]. 茶叶科学, 2010(06):407-413.
[40]李哲, 朱松, 王洪新.酶法酰化儿茶素EGCG及其产物在大豆油中的抗氧化性[J]. 食品科学, 2013(08):1-5.
[41]Zhu S, Li Y, Li Z, et al.Lipase-catalyzed synthesis of acetylated EGCG and antioxidant properties of the acetylated derivatives[J]. Food Research International, 2014, 56:279-286.
[42]Zhu S, Li Y, Ma C Y, et al.Optimization of lipase-catalyzed synthesis of acetylated EGCG by response surface methodology[J]. Journal of Molecular Catalysis B-Enzymatic, 2013, 97:87-94.
[43]赵峰, 阙付有, 梁京, 等.儿茶素单体EGCG酶法修饰研究及其产物抗氧化活性评价[J]. Nat Prod Res Dev, 2015(03):490-495.
[44]霍清, 杨晓芳, 缪刚.3-O-catechin higher fatty acid ester and preparationmethod thereof: 20140122.
[45]刘飞, 熊政委, 李春华, 等.表没食子儿茶素没食子酸酯分子修饰及抗癌研究进展[J]. 食品科学, 2015(23):321-328.
[46]Okushio K, Suzuki M, Matsumoto N, et al.Identification of (-)-epicatechin metabolites and their metabolic fate in the rat[J].Drug Metabolism and Disposition, 1999, 27(2):309-316
[47]Romanov-Michailidis F, Viton F, Fumeaux R, et al.Epicatechin B-Ring Conjugates: First Enantioselective Synthesis and Evidence for Their Occurrence in Human Biological Fluids[J].Organic Letters, 2012, 14(15):3902-3905
[48]Satoshi K, Ariga T, Takanao M, et al.The syntheses of catechin-glucosides by transglycosylation with leuconostoc-mesenteroides sucrose phosphorylase[J].Bioscience Biotechnology and Biochemistry, 1993, 57(12):2010-2015
[49]Moon Y H, Lee J H, Jhon D Y, et al.Synthesis and characterization of novel quercetin-alpha-D-glucopyranosides using glucansucrase from Leuconostoc mesenteroides[J].Enzyme and Microbial Technology, 2007, 40(5):1124-1129
[50]Funayama M, Nishino K, Hirota A, et al.Enzymatic-synthesis of (+)-catechin-alpha-glucoside and its effect on tyrosinase[J].Bioscience Biotechnology and Biochemistry, 1993, 57(10):1666-1669
[51]Aramsangtienchai P, Chavasiri W, Ito K, et al.Synthesis of epicatechin glucosides by a beta-cyclodextrin glycosyltransferase[J].Journasl of Molecular Catalysis B-Enzymatic, 2011, 73(1-4):27-34
[52]Cho H K, Kim H H, Seo D H, et al.Biosynthesis of (+)-catechin glycosides using recombinant amylosucrase from Deinococcus geothermalis DSM 11300[J].Enzyme and Microbial Technology, 2011, 49(2):246-253
[53]张昕, 字成庭, 王宣军.儿茶素糖苷修饰物研究现状[J]. 中国农业信息, 2016(06):54.
[54]吕海鹏, 林智, 孙业良, et al.Preparation method for epigallocatechin gallate (EGCG)methylated derivatives: 2012.02.08.
[55]吕海鹏, 林智, 谭俊峰, 等.茶叶中EGCG3″Me的研究与开发[J]. 食品工业科技, 2008(12):275-277.
[56]吕海鹏, 孙业良, 林智, 等.表没食子儿茶素没食子酸酯的甲基化分子修饰[J]. 食品科学, 2010(15):139-142.
[57]伍妍俊, 汪小钢, 宛晓春.甲基化EGCG的合成及其在人工模拟胃肠液中的稳定性[J]. 安徽农业大学学报, 2010(04):688-691.
[58]Yanase E, Matsumoto E, Shinoda Y, et al.Synthesis of methyl derivatives of epigallocatechin gallate (EGCg) and their stabilities.[J]. ITE Letters on Batteries, New Technologies and MedicineBatteries, 2005.
[59]Zaveri N T.Synthesis of a 3,4,5-Trimethoxybenzoyl Ester Analogue of Epigallocatechin-3-gallate (EGCG):? A Potential Route to the Natural Product Green Tea Catechin,EGCG[J].Organic Letters, 2001, 3(6):843-846
[60]Lai R H, Zhao W F, Huang Y H, et al.The Synthesis of Methylated Epigallocatechin Gallate[J].Chemistry of Natural Compounds, 2015, 51(3):472-475
[61]Aihara Y, Yoshida A, Furuta T, et al.Regioselective synthesis of methylated epigallocatechin gallate via nitrobenzenesulfonyl (Ns) protecting group[J].Bioorganic & Medicinal Chemistry Letters, 2009, 19(15):4171-4174
[62]Asakawa T, Kawabe Y, Yoshida A, et al.Syntheses of methylated catechins and theaflavins using 2-nitrobenzenesulfonyl group to protect and deactivate phenol[J].J Antibiot (Tokyo), 2016, 69(4):299-312
[63]Park K D, Cho S J.Synthesis and antimicrobial activities of 3-O-alkyl analogues of (+)-catechin: Improvement of stability and proposed action mechanism[J].European Journal of Medicinal Chemistry, 2010, 45(3):1028-1033
[64]Hong S, Liu S B.Targeted acylation for all the hydroxyls of (+)-catechin and evaluation of their individual contribution to radical scavenging activity[J]. Food Chemistry, 2016, 197:415-421.
[65]Lin S F, Lin Y H, Lin M J, et al.Synthesis and structure-activity relationship of 3-O-acylated (-)-epigallocatechins as 5 alpha-reductase inhibitors[J].European Journal of Medicinal Chemistry, 2010, 45(12):6068-6076
[66]Utenova B T, Malterud K E, Rise F.Antioxidant activity of O-protected derivatives of (-)-epigallocatechin-3-gallate: inhibition of soybean and rabbit 15-lipoxygenases[J]. Arkivoc, 2007:6-16.
[67]陈平, 孙东, 郑小明.EGCG棕榈酸酯的制备、结构及其抗氧化活性[J]. 浙江大学学报(理学版), 2003(04):422-425.
[68]孙东, 陈平.EGCG肉豆蔻酸酯的制备、结构及其抗氧化活性[J]. 温州医学院学报, 2006(03):225-227.
[69]Osanai K, Landis-Piwowar K R, Dou Q P, et al.A para-amino substituent on the D-ring of green tea polyphenol epigallocatechin-3-gallate as a novel proteasome inhibitor and cancer cell apoptosis inducer[J].Bioorganic & Medicinal Chemistry, 2007, 15(15):5076-5082
[70]Dutta S, Basak A, Dasgupta S.Synthesis and ribonuclease A inhibition activity of resorcinol and phloroglucinol derivatives of catechin and epicatechin: Importance of hydroxyl groups[J].Bioorganic & Medicinal Chemistry, 2010, 18(17):6538-6546
[71]Fudouji R, Tanaka T, Taguri T, et al.Coupling Reactions of Catechins with Natural Aldehydes and Allyl Alcohols and Radical Scavenging Activities of the Triglyceride-Soluble Products[J].Journal of Agricultural and Food Chemistry, 2009, 57(14):6417-6424
[72]Cruz L, Borges E, Silva A M S, et al.Synthesis of a New (+)-Catechin-Derived Compound: 8-Vinylcatechin[J]. Letters in Organic Chemistry, 2008(5):530-536.
[73]Bernini R, Cacchi S, De Salve I, et al.Synthesis of 8-arylated catechin and epicatechin derivatives via Suzuki cross-coupling[J].Tetrahedron Letters, 2007, 48(29):4973-4976
[74]Tanaka T, Kusano R, Kouno I.Synthesis and antioxidant activity of novel amphipathic derivatives of tea polyphenol[J]. Bioorganic&Medicinal Chemistry Letters, 1998(8):1801-1806.
[75]Mull E S, Van Zandt M, Golebiowski A, et al.A versatile approach to the regioselective synthesis of diverse (?)-epicatechin-β-d-glucuronides[J].Tetrahedron Letters, 2012, 53(12):1501-1503
[76]Zhang X, Wang J, Hu J M, et al.Synthesis and Biological Testing of Novel Glucosylated Epigallocatechin Gallate (EGCG) Derivatives[J]. Molecules, 2016, 21(5).
[77]Furuta T, Hirooka Y, Abe A, et al.Concise synthesis of dideoxy-epigallocatechin gallate (DO-EGCG) and evaluation of its anti-influenza virus activity?[J].Bioorganic & Medicinal Chemistry Letters, 2007, 17(11):3095-3098
[78]Yoshida A, Hirooka Y, Sugata Y, et al.Concise synthesis of catechin probes enabling analysis and imaging of EGCg[J].Chem. Commun., 2011, 47(6):1794-1796
[79]Maeda-Yamamoto M, Inagaki N, Kitaura J, et al.O-methylated catechins from tea leaves inhibit multiple protein kinases in mast cells[J].Journal of Immunology, 2004, 172(7):4486-4492
[80]刘晓辉, 江和源, 张建勇, 等.儿茶素酰基化修饰研究进展[J]. 茶叶科学, 2009(01):1-8.