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Pathway Description
Sesquiterpenoid Biosynthesis
Arabidopsis thaliana
Metabolic Pathway
Sesquiterpenoids have 15 carbons and three isoprene units. They are derived from farnesyl diphosphate. They may contain rings or be acyclic, depending on the bonds formed by the loss of the diphosphate group.
First, the terpenoid backbone is synthesized, producing farnesyl pyrophosphate. Two molecules of farnesyl pyrophosphate then join together to form presqualene diphosphate, catalyzed by squalene synthase 1. Then, the same enzyme removes the pyrophosphate group and replaces it with a hydrogen ion, forming squalene. Squalene then undergoes oxidation of one of its bonds via squlene monooxygenase 1, to form (S)-2,3-epoxysqualene. This may then proceed to the steroid biosynthesis pathway or may react with an isomerase or lyase to form a chair-chair-chair-boat triterpenoid. Similarly, squalene may interact with an isomerase or lyase to form a chair-chair-chair-chair triterpenoid.
After the backbone is complete, farnesyl pyrophosphate can have its pyrophosphate removed by different enzymes, leading to different conformations of sesquiterpenoids. If it interacts with (Z)-gamma-bisabolene synthase, it forms gamma-bisabolene. If it interacts wtih (+)-alpha-barbatene synthase, it forms (+)-alpha-barbatene, if it interacts wtih beta-chamigrene synthase it forms (+)-beta-chamigrene, and finally if it interacts with thujopsene synthase it forms (+)-thujopsene.
References
Sesquiterpenoid Biosynthesis References
Crock J, Wildung M, Croteau R: Isolation and bacterial expression of a sesquiterpene synthase cDNA clone from peppermint (Mentha x piperita, L.) that produces the aphid alarm pheromone (E)-beta-farnesene. Proc Natl Acad Sci U S A. 1997 Nov 25;94(24):12833-8. doi: 10.1073/pnas.94.24.12833.
Pubmed: 9371761
Nagegowda DA, Gutensohn M, Wilkerson CG, Dudareva N: Two nearly identical terpene synthases catalyze the formation of nerolidol and linalool in snapdragon flowers. Plant J. 2008 Jul;55(2):224-39. doi: 10.1111/j.1365-313X.2008.03496.x. Epub 2008 Mar 19.
Pubmed: 18363779
Bertea CM, Voster A, Verstappen FW, Maffei M, Beekwilder J, Bouwmeester HJ: Isoprenoid biosynthesis in Artemisia annua: cloning and heterologous expression of a germacrene A synthase from a glandular trichome cDNA library. Arch Biochem Biophys. 2006 Apr 15;448(1-2):3-12. doi: 10.1016/j.abb.2006.02.026. Epub 2006 Mar 15.
Pubmed: 16579958
de Kraker JW, Franssen MC, Joerink M, de Groot A, Bouwmeester HJ: Biosynthesis of costunolide, dihydrocostunolide, and leucodin. Demonstration of cytochrome p450-catalyzed formation of the lactone ring present in sesquiterpene lactones of chicory. Plant Physiol. 2002 May;129(1):257-68. doi: 10.1104/pp.010957.
Pubmed: 12011356
Jaroszewski JW, Strom-Hansen T, Hansen SH, Thastrup O, Kofod H: On the botanical distribution of chiral forms of gossypol. Planta Med. 1992 Oct;58(5):454-8. doi: 10.1055/s-2006-961512.
Pubmed: 17226502
Steele CL, Crock J, Bohlmann J, Croteau R: Sesquiterpene synthases from grand fir (Abies grandis). Comparison of constitutive and wound-induced activities, and cDNA isolation, characterization, and bacterial expression of delta-selinene synthase and gamma-humulene synthase. J Biol Chem. 1998 Jan 23;273(4):2078-89. doi: 10.1074/jbc.273.4.2078.
Pubmed: 9442047
Fraga BM: Natural sesquiterpenoids. Nat Prod Rep. 2008 Dec;25(6):1180-209. doi: 10.1039/b806216c. Epub 2008 Oct 14.
Pubmed: 19030608
Field B, Fiston-Lavier AS, Kemen A, Geisler K, Quesneville H, Osbourn AE: Formation of plant metabolic gene clusters within dynamic chromosomal regions. Proc Natl Acad Sci U S A. 2011 Sep 20;108(38):16116-21. doi: 10.1073/pnas.1109273108. Epub 2011 Aug 29.
Pubmed: 21876149
Field B, Osbourn AE: Metabolic diversification--independent assembly of operon-like gene clusters in different plants. Science. 2008 Apr 25;320(5875):543-7. doi: 10.1126/science.1154990. Epub 2008 Mar 20.
Pubmed: 18356490
Qi X, Bakht S, Leggett M, Maxwell C, Melton R, Osbourn A: A gene cluster for secondary metabolism in oat: implications for the evolution of metabolic diversity in plants. Proc Natl Acad Sci U S A. 2004 May 25;101(21):8233-8. doi: 10.1073/pnas.0401301101. Epub 2004 May 17.
Pubmed: 15148404
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