Caffeoyl-quinic acid

Chlorogenic acid lactones are produced in roasted coffee and range from 1.5 to 3.5 g/kg in commercial roasted coffee samples. Two lactones that have been identified in roasted coffee are 3-caffeoyl- and 4-caffeoyl-quinic acid-y-lactone.60... 

Scarpati, M. L. and Guiso, M., Caffeoyl-quinic acid from coffee and mate, Ann Chim (Rome) 53, 1315, 1963. 

Caffeoyl-quinic acid, 3-5-di-O Sd Al04 Caffeoyl-quinic acid, 4 Sd " ° °... 

Green coffee beans (Coffea arabica) are one of the richest dietary sources of chlorogenic acids. 5-O-Caffeoylquinic acid is the dominant chlorogenic acid accounting for 50% of the total. This is followed by 3-0- and 4-O-caffeoyl-quinic acid, the three analogous feruloylquinic acids and 3,4-0-, 3,5-0- and 4,5-O-dicaffeoylquinic acids (Fig. 1.32) [Clifford, 1999]. Levels decline ca. 80% during the roasting of coffee beans, but sizable amounts with substantial antioxidant activity are still found in the typical cup of coffee. 

Parejo et al. (2004) identified caffeoyl-quinic acids, dicaffeoylquinic acids, flavonoids and rosmarinic acid among ten main antioxidant phenolic compounds from bitter fennel, F. vulgare, using a simple high-performance liquid chromatography (HPLC). Distilled fennel was found to contain a higher proportion of antioxidant phenolic compounds than non-distilled plant material. 

R H H H pseudo chlorogeiiic acid (l-O-caffeoyl quinic acid)... 

Ri 0.4-0.5 blue caffeoyl quinic acids (e.g. chlorogenic acid, Tl)... 

C. fructus (2) shows very weak zones of caffeoyl quinic acids and hypero.side only. 

Caffeic acid derivatives Caffeic acid (110), Chloro-genic acid (111) its butyl ester, Rosmarinic acid (112), KOP (Caffeic acid oxidised polymer). 3,4,5-Tri-O-caffeoyl-quinic acid, 4,5-Di-O -caffeoylquinic acid, Synapoic acid Many sp. Securidaca longipedunculala HSV HIV Virucidal, Cellular DNA metabolism. Binding of gpl20 to CD4 HIV-RT [16. 73, 74] [75, 76]... 

Phenolic compounds include a wide range of secondary metabolites that are biosynthesised from carbohydrates through the shikimate pathway [14]. This is the biosynthetic route to the aromatic amino acids, phenylalanine, tyrosine, and tryptophan, and only occurs in microorganisms and plants. In the first step, the glycolytic intermediate phosphoenol pyruvate and the pentose phosphate intermediate erythrose-4-phosphate are condensed to 3-deoxy-D-arabino-heptulosonate 7-phosphate (DAHP), a step catalysed by DAHP synthase. Intermediates of the shikimate pathway are 3-dehydroquinate, shikimate, and chorismate (Fig. 1). Phenylalanine is biosynthesised from chorismate, and from phenylalanine all the phenylpropanoids. Quinate is produced from 3-dehydroquinate and incorporated into chlorogenic and isochlorogenic acids (caffeoyl quinic acids) by combination with caffeic acid. Gallic acid is produced from shikimate. 

Luo J, Butelli E, Hill L, Parr A, Niggeweg R, Bailey P, Weisshaar B, Martin C (2008) AtMYB 12 regulates caffeoyl quinic acid and fiavonol synthesis in tomato expression in fiuit results in very high levels of both types of polyphenol. Plant J 56 316-326... 

Luteolin-glycosides (<1%) caffeoyl-quinic acids (<2%) sesquiterpene lactones (<4%) Anthocyanins (mainly malvidin, cyanidin, and delphinidin glycosides) (<24%) Isoquercitrin, rutin, narcissin ... 

Esters of phenolic acids, particularly the hydroxycinnamic acids (9, 12, 13 and 14), with (—)-quinic acid, (—)-shikimic acid and D-glucose are also widely distributed in the plant kingdon Chlorogenic acid (23), 5-O-caffeoyl-quinic acid, is for example... 

The aim of this study was the development of conversion system of caffeoylquinic acids to valuable compounds. When an IL, l-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([bmim][NTf2]) was used as a reaction solvent, we found that immobilized chlorogenate hydrolase (Kikkoman) catalyzed the conversion of 5-caffeoylquinic acid to methyl caffeate with methanol (Fig. 1). The immobilized enzyme was prepared with chlorogenate hydrolase using quaternary ammonium sepabeads (Mitsubishi Chemical Co., Tokyo, Japan) (Kurata et al., 2011). To synthesize valuable compounds from caffeoylquinic adds, we attempted to develop a method for the conversion of caffeoylquinic acids to CAPE analogues via methyl caffeate. In section 2, we describe the properties of immobilised chlorogenate hydrolase in ILs. Using various caffeoyl quinic acid prepared from immature coffee beans, we developed a system to produce methyl caffeate. 

---