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Pathway Description
Coumarin Biosynthesis
Arabidopsis thaliana
Category:
Metabolite Pathway
Sub-Category:
Metabolic
Created: 2025-11-27
Last Updated: 2026-01-28
This pathway describes the conversion of L-phenylalanine into a diverse suite of coumarins in Arabidopsis thaliana, tracing a major branch of phenylpropanoid metabolism that supports defense, stress adaptation, and iron acquisition. Beginning with the deamination of L-phenylalanine to trans-cinnamic acid, the pathway proceeds through successive hydroxylation and CoA-activation steps to generate key intermediates such as p-coumarate, caffeate, ferulate, and their corresponding CoA esters. From these central phenylpropanoid nodes, the pathway branches into the biosynthesis of simple and highly oxidized coumarins. Lactonization of caffeoyl-CoA yields esculetin, while hydroxylation and intramolecular cyclization of feruloyl-CoA produce scopoletin, which can be further methylated or oxidized to form scoparone, fraxetin, and finally sideretin, a major coumarin involved in iron mobilization in the rhizosphere. Several alternative or parallel reactions allow interchange between free acids and CoA esters—such as the conversions between p-coumarate, caffeate, p-coumaroyl-CoA, and caffeoyl-CoA—reflecting enzymatic flexibility in the phenylpropanoid network. Together, these reactions form a coherent metabolic route linking amino-acid–derived precursors to specialized coumarin metabolites that play essential biochemical and ecological roles in plants.
References
Coumarin Biosynthesis References
Wang Y, Guan T, Yue X, Yang J, Zhao X, Chang A, Yang C, Fan Z, Liu K, Li Y: The biosynthetic pathway of coumarin and its genetic regulation in response to biotic and abiotic stresses. Front Plant Sci. 2025 Jun 19;16:1599591. doi: 10.3389/fpls.2025.1599591. eCollection 2025.
Pubmed: 40612619
Robe K, Conejero G, Gao F, Lefebvre-Legendre L, Sylvestre-Gonon E, Rofidal V, Hem S, Rouhier N, Barberon M, Hecker A, Gaymard F, Izquierdo E, Dubos C: Coumarin accumulation and trafficking in Arabidopsis thaliana: a complex and dynamic process. New Phytol. 2021 Feb;229(4):2062-2079. doi: 10.1111/nph.17090. Epub 2020 Dec 16.
Pubmed: 33205512
Fraser CM, Chapple C: The phenylpropanoid pathway in Arabidopsis. Arabidopsis Book. 2011;9:e0152. doi: 10.1199/tab.0152. Epub 2011 Dec 6.
Pubmed: 22303276
Wanner LA, Li G, Ware D, Somssich IE, Davis KR: The phenylalanine ammonia-lyase gene family in Arabidopsis thaliana. Plant Mol Biol. 1995 Jan;27(2):327-38. doi: 10.1007/bf00020187.
Pubmed: 7888622
Cochrane FC, Davin LB, Lewis NG: The Arabidopsis phenylalanine ammonia lyase gene family: kinetic characterization of the four PAL isoforms. Phytochemistry. 2004 Jun;65(11):1557-64. doi: 10.1016/j.phytochem.2004.05.006.
Pubmed: 15276452
Lin X, Kaul S, Rounsley S, Shea TP, Benito MI, Town CD, Fujii CY, Mason T, Bowman CL, Barnstead M, Feldblyum TV, Buell CR, Ketchum KA, Lee J, Ronning CM, Koo HL, Moffat KS, Cronin LA, Shen M, Pai G, Van Aken S, Umayam L, Tallon LJ, Gill JE, Adams MD, Carrera AJ, Creasy TH, Goodman HM, Somerville CR, Copenhaver GP, Preuss D, Nierman WC, White O, Eisen JA, Salzberg SL, Fraser CM, Venter JC: Sequence and analysis of chromosome 2 of the plant Arabidopsis thaliana. Nature. 1999 Dec 16;402(6763):761-8. doi: 10.1038/45471.
Pubmed: 10617197
Bell-Lelong DA, Cusumano JC, Meyer K, Chapple C: Cinnamate-4-hydroxylase expression in Arabidopsis. Regulation in response to development and the environment. Plant Physiol. 1997 Mar;113(3):729-38. doi: 10.1104/pp.113.3.729.
Pubmed: 9085570
Mizutani M, Ohta D, Sato R: Isolation of a cDNA and a genomic clone encoding cinnamate 4-hydroxylase from Arabidopsis and its expression manner in planta. Plant Physiol. 1997 Mar;113(3):755-63. doi: 10.1104/pp.113.3.755.
Pubmed: 9085571
Lee D, Ellard M, Wanner LA, Davis KR, Douglas CJ: The Arabidopsis thaliana 4-coumarate:CoA ligase (4CL) gene: stress and developmentally regulated expression and nucleotide sequence of its cDNA. Plant Mol Biol. 1995 Aug;28(5):871-84. doi: 10.1007/bf00042072.
Pubmed: 7640359
Ehlting J, Buttner D, Wang Q, Douglas CJ, Somssich IE, Kombrink E: Three 4-coumarate:coenzyme A ligases in Arabidopsis thaliana represent two evolutionarily divergent classes in angiosperms. Plant J. 1999 Jul;19(1):9-20.
Pubmed: 10417722
Theologis A, Ecker JR, Palm CJ, Federspiel NA, Kaul S, White O, Alonso J, Altafi H, Araujo R, Bowman CL, Brooks SY, Buehler E, Chan A, Chao Q, Chen H, Cheuk RF, Chin CW, Chung MK, Conn L, Conway AB, Conway AR, Creasy TH, Dewar K, Dunn P, Etgu P, Feldblyum TV, Feng J, Fong B, Fujii CY, Gill JE, Goldsmith AD, Haas B, Hansen NF, Hughes B, Huizar L, Hunter JL, Jenkins J, Johnson-Hopson C, Khan S, Khaykin E, Kim CJ, Koo HL, Kremenetskaia I, Kurtz DB, Kwan A, Lam B, Langin-Hooper S, Lee A, Lee JM, Lenz CA, Li JH, Li Y, Lin X, Liu SX, Liu ZA, Luros JS, Maiti R, Marziali A, Militscher J, Miranda M, Nguyen M, Nierman WC, Osborne BI, Pai G, Peterson J, Pham PK, Rizzo M, Rooney T, Rowley D, Sakano H, Salzberg SL, Schwartz JR, Shinn P, Southwick AM, Sun H, Tallon LJ, Tambunga G, Toriumi MJ, Town CD, Utterback T, Van Aken S, Vaysberg M, Vysotskaia VS, Walker M, Wu D, Yu G, Fraser CM, Venter JC, Davis RW: Sequence and analysis of chromosome 1 of the plant Arabidopsis thaliana. Nature. 2000 Dec 14;408(6814):816-20. doi: 10.1038/35048500.
Pubmed: 11130712
Schoch G, Goepfert S, Morant M, Hehn A, Meyer D, Ullmann P, Werck-Reichhart D: CYP98A3 from Arabidopsis thaliana is a 3'-hydroxylase of phenolic esters, a missing link in the phenylpropanoid pathway. J Biol Chem. 2001 Sep 28;276(39):36566-74. doi: 10.1074/jbc.M104047200. Epub 2001 Jun 27.
Pubmed: 11429408
Cheng CY, Krishnakumar V, Chan AP, Thibaud-Nissen F, Schobel S, Town CD: Araport11: a complete reannotation of the Arabidopsis thaliana reference genome. Plant J. 2017 Feb;89(4):789-804. doi: 10.1111/tpj.13415. Epub 2017 Feb 10.
Pubmed: 27862469
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