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MetaCyc Pathway: superpathway of anthocyanin biosynthesis (from delphinidin 3-O-glucoside)
Inferred from experiment

Pathway diagram: superpathway of anthocyanin biosynthesis (from delphinidin 3-O-glucoside)

If an enzyme name is shown in bold, there is experimental evidence for this enzymatic activity.

Superclasses: BiosynthesisSecondary Metabolites BiosynthesisPhenylpropanoid Derivatives BiosynthesisFlavonoids BiosynthesisAnthocyanins Biosynthesis

Some taxa known to possess this pathway include : Clitoria ternatea, Gentiana triflora, Ipomoea nil, Ipomoea purpurea, Perilla frutescens

Expected Taxonomic Range: Spermatophyta

General Background

The superpathway of anthocyanin biosynthesis that originates from delphinidin 3-O-glucoside comprises the formation of compounds such as ternatin C5, anthocyanidin sophoroside and gentiodelphin. Those anthocyanins are usually very stable pigments contributing to a wide variation of flower colors in different species.

Ternatins are a group of 15 polyacetylated delphinidin glucosides that confer blue color to the petals of butterfly pea ( Clitoria ternatea). The general structure of ternatins consists of malonylated delphinidin 3,3',5'-triglucosides having 3',5'-side chains with alternating D-glucose and p-coumaric acid units of varying lengths [Terahara96, Kazuma03].

Antocyanidins often occur as sophoroside, i.e. a diglucoside that consists of glucose attached to the 2''-O-position of the 3-O-glucose moiety of anthocyanidins. The anthocyanidin that confers the bright blue color to Ipomoea nil (a member of the Convolvulacea) is a sophoroside that forms a complex with several caffeoyl residues, known as Wedding Bells anthocyanin (WBA). Reddish-brown flowers of dusky mutants of Ipomoea nil contain Heavenly Blue antocyanin (HBA) representing the most favorite flower hue for Japanese floriculturists [Morita05].

Gentiodelphin, i.e. delphinidin 3-O-glucosyl-5-O-caffeoylglucoside-3'-O-caffeoylglucoside found in the genus Gentiana is a unusual stable anthocyanin conferring deep blue flower colors to this species [Goto82]. The stability of this compound has been proposed as an effect of the intramolecular stacking of acyl residues attached to the opposite sides of the A and B-ring sandwiching the corresponding anthocyanidin [Yoshida91].

About This Pathway

Ternatin C5: The simplest ternatin is ternatin C5 that is the starting point for the formation of the most complex ternatin, i.e. ternatin A1 and its intermediates. The characteristic glucosylation pattern of ternatins, the 3,3',5'-triglucosylated delphinidin is formed by the catalytic activity of 3' and 5'-position specific glucosyltransferases [Kazuma04] thought to be involved in the early biosynthetic pathway of ternatins following the 6''-O-malonysation of the delphinidin 3-O-glucoside.

Anthocyanin sophoroside: The crucial step in the formation of anthocyanidin sophoroside as precursors for HBA and WBA in Ipomoea is catalyzed by the anthocyanidin 3-O-glucoside 2-O''-glucosyltransferase (3GGT). The enzyme adds glucose to anthocyanidin 3-glucosides at the 2''-O-position of the glucose moiety forming the corresponding sophorosides. Although the enzyme accepts all three major anthocyanidin 3-O-glucoside, anthocyanidin 3,5-diglucoside are not suitable substrates for the 3GGT [Morita05].

Gentiodelphin: The first committed step in the gentiodelphin biosynthesis is the 5-O-glucosylation of delphinidin 3-O-glucoside. The next steps that further decorate delphinidin 3,5-glucoside with caffeic acid and glucose are proposed to constitute a metabolic grid in the biosynthetic route towards gentiodelphin. Both possible routes, i.e. 3'-O-glucosylation followed by the aromatic 5-O-acylation or vice versa are displayed and thought to be present in Gentiana [Fujiwara98a, FukuchiMizutani03]. The glucosyltransferases involved in the biosynthesis of gentiodelphin are highly position specific and follow a defined order which is the 3-O-glucosylation followed by the 5-O-glucosylation and the subsequent 3'-O-glucosylation of the delphinidin backbone [FukuchiMizutani03]. The 5-aromatic acyltransferase [Fujiwara97, Fujiwara98a] can only acylate the 5-O-glucoside but not the 3, 7 or 3' positions of anthocyanins.

Subpathways: gentiodelphin biosynthesis, ternatin C5 biosynthesis

Created 06-Sep-2006 by Foerster H, TAIR


Fujiwara97: Fujiwara H, Tanaka Y, Fukui Y, Nakao M, Ashikari T, Kusumi T (1997). "Anthocyanin 5-aromatic acyltransferase from Gentiana triflora. Purification, characterization and its role in anthocyanin biosynthesis." Eur J Biochem 249(1);45-51. PMID: 9363752

Fujiwara98a: Fujiwara H, Tanaka Y, Yonekura-Sakakibara K, Fukuchi-Mizutani M, Nakao M, Fukui Y, Yamaguchi M, Ashikari T, Kusumi T (1998). "cDNA cloning, gene expression and subcellular localization of anthocyanin 5-aromatic acyltransferase from Gentiana triflora." Plant J 16(4);421-31. PMID: 9881162

FukuchiMizutani03: Fukuchi-Mizutani M, Okuhara H, Fukui Y, Nakao M, Katsumoto Y, Yonekura-Sakakibara K, Kusumi T, Hase T, Tanaka Y (2003). "Biochemical and molecular characterization of a novel UDP-glucose:anthocyanin 3'-O-glucosyltransferase, a key enzyme for blue anthocyanin biosynthesis, from gentian." Plant Physiol 132(3);1652-63. PMID: 12857844

Goto82: Goto T, Kondo T, Tamura H, Imagawa H (1982). "Structure of gentiodelphin, an acylated anthocyanin isolated from Gentiana makinoi, that is stable in dilute aqueous solution." Tetrahedron Letters, 23(36), 3695-3698.

Kazuma03: Kazuma K, Noda N, Suzuki M (2003). "Malonylated flavonol glycosides from the petals of Clitoria ternatea." Phytochemistry 62(2);229-37. PMID: 12482461

Kazuma04: Kazuma K, Kogawa K, Noda N, Kato N, Suzuki M (2004). "Identification of Delphinidin 3-O-(6''-O-Malonyl)-beta-glucoside-3'-O-beta-glucoside, a Postulated Intermediate in the Biosynthesis of Ternatin C5 in the Blue Petals of Clitoria ternatea (Butterfly Pea)." Chemistry & Bioderversity, 1, 1762-1770.

Morita05: Morita Y, Hoshino A, Kikuchi Y, Okuhara H, Ono E, Tanaka Y, Fukui Y, Saito N, Nitasaka E, Noguchi H, Iida S (2005). "Japanese morning glory dusky mutants displaying reddish-brown or purplish-gray flowers are deficient in a novel glycosylation enzyme for anthocyanin biosynthesis, UDP-glucose:anthocyanidin 3-O-glucoside-2''-O-glucosyltransferase, due to 4-bp insertions in the gene." Plant J 42(3);353-63. PMID: 15842621

Terahara96: Terahara N, Oda M, Matsui T, Osajima Y, Saito N, Toki K, Honda T (1996). "Five new anthocyanins, ternatins A3, B4, B3, B2, and D2, from Clitoria ternatea flowers." J Nat Prod 59(2);139-44. PMID: 8991946

Yoshida91: Yoshida K, Kondo T, Goto T (1991). "Unusually stable monoacylated anthocyanin from purple yam Dioscorea alata." Tetrahedron Letters, 32(40), 5579-5580.

Other References Related to Enzymes, Genes, Subpathways, and Substrates of this Pathway

Ellestad06: Ellestad GA (2006). "Structure and chiroptical properties of supramolecular flower pigments." Chirality 18(2);134-44. PMID: 16385618

Kazuma03a: Kazuma K, Noda N, Suzuki M (2003). "Flavonoid composition related to petal color in different lines of Clitoria ternatea." Phytochemistry 64(6);1133-9. PMID: 14568080

Kogawa06: Kogawa K, Kazuma K, Kato N, Noda N, Suzuki M (2006). "Biosynthesis of malonylated flavonoid glycosides on the basis of malonyltransferase activity in the petals of Clitoria ternatea." J Plant Physiol NIL. PMID: 16887235

Kogawa07: Kogawa K, Kato N, Kazuma K, Noda N, Suzuki M (2007). "Purification and characterization of UDP-glucose: anthocyanin 3',5'-O-glucosyltransferase from Clitoria ternatea." Planta 226(6);1501-9. PMID: 17668234

Latendresse13: Latendresse M. (2013). "Computing Gibbs Free Energy of Compounds and Reactions in MetaCyc."

Lazarowski03: Lazarowski ER, Shea DA, Boucher RC, Harden TK (2003). "Release of cellular UDP-glucose as a potential extracellular signaling molecule." Mol Pharmacol 63(5);1190-7. PMID: 12695547

Lima96: Lima MA, Silveira ER, Marques MS, Santos RH, Gambardela MT (1996). "Biologically active flavonoids and terpenoids from Egletes viscosa." Phytochemistry 41(1);217-23. PMID: 8588867

Mizutani06: Mizutani M, Katsumoto Y, Fukui Y, Togami J, Nakamura N, Okuhara H (2006). "An acyltransferase involved in biosynthesis of polyacylated anthocyanin." Plant Cell Physiol 47 supplement s198.

Nakatsuka08: Nakatsuka T, Sato K, Takahashi H, Yamamura S, Nishihara M (2008). "Cloning and characterization of the UDP-glucose:anthocyanin 5-O-glucosyltransferase gene from blue-flowered gentian." J Exp Bot 59(6);1241-52. PMID: 18375606

Rubio06: Rubio S, Larson TR, Gonzalez-Guzman M, Alejandro S, Graham IA, Serrano R, Rodriguez PL (2006). "An Arabidopsis mutant impaired in coenzyme A biosynthesis is sugar dependent for seedling establishment." Plant Physiol 140(3);830-43. PMID: 16415216

Suzuki02: Suzuki H, Nakayama T, Yonekura-Sakakibara K, Fukui Y, Nakamura N, Yamaguchi MA, Tanaka Y, Kusumi T, Nishino T (2002). "cDNA cloning, heterologous expressions, and functional characterization of malonyl-coenzyme a:anthocyanidin 3-o-glucoside-6"-o-malonyltransferase from dahlia flowers." Plant Physiol 130(4);2142-51. PMID: 12481098

Suzuki03a: Suzuki M (2003). "The DNA-binding specificity of eubacterial and archaeal FFRPs.." Proceedings of the Japan Academy, Series B79B(7); 213-222.

Suzuki04: Suzuki H, Nakayama T, Yamaguchi M, Nishino T (2004). "cDNA cloning and characterization of two Dendranthema morifoliumanthocyanin malonyltransferases with different functional activities." Plant Science 166:89-96.

Tanaka11: Tanaka Y, Katsumoto Y, Mizutani M, Fukui Y, Togami J (2011). "Stabilization and blueing of anthocyanin pigments using gene encoding aromatic acyltransferase capable of transferring an aromatic acyl group to the 3'-position of anthocyanins." US patent 8,053,634 B2.

Terahara98: Terahara N, Toki K, Saito N, Honda T, Matsui T, Osajima Y (1998). "Eight new anthocyanins, ternatins C1-C5 and D3 and preternatins A3 and C4 from young Clitoria ternatea flowers." J Nat Prod 61(11);1361-7. PMID: 9834153

Yamazaki99: Yamazaki M, Gong Z, Fukuchi-Mizutani M, Fukui Y, Tanaka Y, Kusumi T, Saito K (1999). "Molecular cloning and biochemical characterization of a novel anthocyanin 5-O-glucosyltransferase by mRNA differential display for plant forms regarding anthocyanin." J Biol Chem 274(11);7405-11. PMID: 10066805

Yoshida00: Yoshida K, Toyama Y, Kameda K, Kondo T (2000). "Contribution of each caffeoyl residue of the pigment molecule of gentiodelphin to blue color development." Phytochemistry 54(1);85-92. PMID: 10846752

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Please cite the following article in publications resulting from the use of MetaCyc: Caspi et al, Nucleic Acids Research 42:D459-D471 2014
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