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Review Article Caffeates and Caffeamides: Synthetic Methodologies and Their Antioxidant Properties

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Review Article Caffeates and Caffeamides: Synthetic Methodologies and Their Antioxidant Properties Hindawi International Journal of Medicinal Chemistry Volume 2019, Article ID 2592609, 15 pages https://doi.org/10.1155/2019/2592609 Review Article Caffeates and Caffeamides: Synthetic Methodologies and Their Antioxidant Properties Merly de Armas-Ricard ,1 Enrique Ruiz-Reyes,2 and Oney Ramírez-Rodríguez 1 1Laboratory of Chemistry and Biochemistry, Campus Lillo, University of Aysén, Eusebio Lillo 667, Coyhaique 5951537, Aysén, Chile 2Department of Chemistry, Basic Sciences Institute, Technical University of Manabí (Universidad Técnica de Manabí), Av Urbina y Che Guevara, Portoviejo, Manabí, Ecuador Correspondence should be addressed to Merly de Armas-Ricard; [email protected] and Oney Ramírez-Rodríguez; [email protected] Received 29 April 2019; Accepted 25 July 2019; Published 11 November 2019 Academic Editor: Rosaria Volpini Copyright © 2019 Merly de Armas-Ricard et al. ­is is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. Polyphenols are secondary metabolites of plants and include a variety of chemical structures, from simple molecules such as phenolic acids to condensed tannins and highly polymerized compounds. Caeic acid (3,4-dihydroxycinnamic acid) is one of the hydroxycinnamate metabolites more widely distributed in plant tissues. It is present in many food sources, including coee drinks, blueberries, apples, and cider, and also in several medications of popular use, mainly those based on propolis. Its derivatives are also known to possess anti-inammatory, antioxidant, antitumor, and antibacterial activities, and can contribute to the prevention of atherosclerosis and other cardiovascular diseases. ­is review is an overview of the available information about the chemical synthesis and antioxidant activity of caeic acid derivatives. Considering the relevance of these compounds in human health, many of them have been the focus of reviews, taking as a center their obtaining from the plants. ­ere are few revisions that compile the chemical synthesis methods, in this way, we consider that this review does an important contribution. 1. Introduction blueberries, apples, and cider [26], and also in several medica- tions of popular use, mainly those based on propolis. Its deriv- Polyphenols are secondary metabolites of plants and include atives are also known to possess anti-inammatory [27, 28], a variety of chemical structures, from simple molecules such antioxidant [29–31], antitumor [32–39] and antibacterial activ- as phenolic acids to condensed tannins and highly polymer- ities [40–42], and can contribute to the prevention of athero- ized compounds. ­e benets of polyphenols on human sclerosis and other cardiovascular diseases [30, 43]. health are oen ascribed to their potential ability to act as Although there are many literature reports that address antioxidants [1, 2]. ­e phenolic derivatives, such as caeic the dierent caeate biological activities, much research acid, catechol, catechin, vanillic acid, eugenol, and thymol, act remains to be done on this family of polyphenols, and new as natural antimicrobial agents. As components of herbs and derivatives with potentially higher activity than natural or spices, that oen provide unique avoring properties, many synthetic products reported can be obtained. In this review, of these compounds have been used by humans for centuries. we will show several synthetic methods and the antioxidant ­ese agents protect human health and extend the shelf life activity of these compounds. of foods [3]. Catechol derivateives with antitumor [4–14], antifungal [15] and antibacterial [16–23] activities, among others [24, 25], have been reported in the literature. 2. Chemical Synthesis of Caffeic Acid ­ere are two fundamental classes of phenolic acids, Derivatives hydroxycinnamics (C6–C3) and hydroxybenzoics (C6–C1). Caeic acid (3,4-dihydroxycinnamic acid) is one of the hydrox- Polyphenol and its derivatives may be obtained through ycinnamate metabolites more widely distributed in plant tis- organic synthesis methodologies from caeic acid itself or sues. It is present in many food sources, including coee drinks, from other chemical precursors. 2 International Journal of Medicinal Chemistry N - O O PF 6 NHR R N HO 2 3 HO R2 OH N N N(CH3)2 BOP/NEt O 3 R3 P N(CH3)2 HO DMF/CH2Cl2 HO BOP reagent N(CH3)2 DCC, Amine RT or reux N C N O HO R DCC reagent N H HO CH3 . N N C N CH3 HCl N H3C N N N EDC reagent - PF - N N 6 Cl O N HATU reagent N N O Cl O n OH NH2 OAc O OTBS HO H3CO HO OAc Cl Cl OTBS O n= 1, 2, 3, 5, 7, 10 OCH3 CH Cl , HATU, 2 2 EDC/DMAP/CH Cl N,N-diisopropylethylamine, 2 2 r.t.,overnight OAc H O N OTBS OAc Cl O n O H CO O O 3 OTBS Cl Cl n= 1, 2, 3, 5, 7, 10 OCH3 F«¬®¯° 1: Synthesis of caeic acid amides using some coupling reagents. Caeic acid amides and esters have been synthesized by prepare amides and esters [62, 63]. Yang et al. [58] synthesize several methods. One of the most common methods is from N-Propargyl caeate amide (PACA) transforming this com- caeic acid using coupling reagents, such as (benzotri- pound into di-O-acetyl-caeic acid N-hydroxysuccinimide azol-1-yloxy)tris(dimethylamino)phosphonium hexauoro- ester via the reaction with N,N -disuccinimidyl carbonate in phosphate (BOP reagent), dicyclohexylcarbodiimide (DCC), DMF. ­is ester is transformed in propargyl amide by reaction 1-(bis(dimethylamino)methylene)-1H-[1,2,3]triazolo[4,5-b] with the corresponding amine, which′ simultaneously removes pyridine-1-ium 3-oxide hexauorophosphate (HATU), and the O-acetyl groups (Figure 2). N-Hydroxysuccinimide esters 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochlo- of p-coumaric, ferulic, and caeic acids are used to transfer ride (EDC). Rajan et al. [44], Fu et al. [45], Shi et al. [46], and hydroxycinnamic moiety to other structures. Stoekigt and Jitareanu et al. [47] report the use of BOP to prepare amides Zenk [64] prepared those esters using DCC in dry ethyl acetate from caeic. Fancelli et al. [48], Arliolo et al. [49], Dai et al. and Ishihara et al. [65], using the same protocol, synthesized [50], Misra et al. [41], Chen et al. [51], Misra et al. [40], and Liu avenanthramides (Figure 3). et al. [52], report the use of DCC. Li et al. [53] report the use Di-O-acetyl caeic acid can be transformed into amides HATU, while Kwon et al. [54], Takahashi et al. [55], Chen et al. via acid chloride too [59, 66, 67]. Doiron et al. [67] used [56], and Otero et al. [57] report the use of EDC (Figure 1). acetylated caeic acid to prepare esters and amides; thionyl Other methods use acetylated caeic acid. Caeic acid is chloride with catalytic DMF is preferred to obtain esters, while acetylated with acetic anhydride in basic media (pyridine or cold oxalyl chloride in dichloromethane is preferred in the its derivatives [58–60] or sodium hydroxide [61]) to yield synthesis of the caeamides (Figure 2). ­e acetyl protecting di-O-acetyl caeic acid. ­is intermediate can be used to groups can be removed under basic [58, 62, 63, 67] or acid [53, International Journal of Medicinal Chemistry 3 O O O O O N O O N O O O Ac O/Py O HO 2 OH O O O N OH O O RT/6 h O DMF, 60 °C, 6 h O O HO O O Condition 2 O Condition 1 SOCl Cl 2 Cl DMF, 50 °C, 8 h H N O 2 DMFcat / CH2Cl2 / 0 °C / 3 h O O O O H N N3 Cl AcO N3 2 HO N O N H Py/RT/12 h O H AcO HO O (1) R-NH2/Py, acetone, 0 °C–RT, 20 h; (2) MeOH, THF, HCl, 60 °C, 1 h. O HO R N H HO F«¬®¯° 2: Synthesis of caeic acid amides using di-O-acetyl caeic acid as intermediate. O O O O DCC HO N HO O OH + HO N AcOEt (dry) O HO HO O N-hydroxysuccinimide ester HO COOH Acetone/H2O 24 h HO NH2 OH OH O HO N H COOH HO F«¬®¯° 3: Synthesis of avenanthramides reported by Ishihara et al. [65]. O O O O O O O O S MeO Cl O MeO Cl MeO S OH N nOH N nO H H H N nOH RT MeO 2 MeO MeO RT TPP 130 °C 18 h or 150 °C MW, 90 min O O HO Ph BBr3 MeO Ph N nP N nP H Ph H Ph Ph –70 °C to RT/12 h Ph HO – MeO – CH3SO3 CH3SO3 F«¬®¯° 4: Synthesis of caeic acid derivatives from methylated acid. 4 International Journal of Medicinal Chemistry O O HO TPP/DIAD HO OH + HO R O R THF/RT/2 days HO HO R = 2-(thiophen-2-yl) ethyl, pyridin-4-ylmethyl, pyridin-3-ylmethyl, 2-(pyridin-2-yl) ethyl, pyridin-2-ylmethyl F«¬®¯° 5: Synthesis of caeates by Mitsunobu reaction. O HO O + HO Vinyl ca eate HO Sitosterol Enzyme / 45 °C hexane:2-butanone (9:1, v/v) + HO O O HO O HO Sitosteryl ca eate F«¬®¯° 6: Enzymatic transesterication of vinyl caeate with sitosterol. 59] mild conditions. Other authors use ethyl chloroformate to compounds are caeic acid and 3,4-dihydroxybenzaldehyde. obtain amides from protected caeic acid (Figure 4) [68, 69]. From caeic acid, some authors synthesize alkyl caeates by Hydroxyl groups of caeic acid can be protected by meth- nucleophilic displacement of a halogen atom from an alkyl ylation too. Amides can be synthesized by all methods already halide in a basic medium [60, 73].
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