Reaction: (2E,6E)-farnesyl diphosphate = aristolochene + diphosphate
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Other name(s): sesquiterpene cyclase; trans,trans-farnesyl diphosphate aristolochene-lyase; trans,trans-farnesyl-diphosphate diphosphate-lyase (cyclizing, aristolochene-forming); 2-trans,6-trans-farnesyl-diphosphate diphosphate-lyase (cyclizing, aristolochene-forming)
Systematic name: (2E,6E)-farnesyl-diphosphate diphosphate-lyase (cyclizing, aristolochene-forming)
Comments: The initial internal cyclization produces the monocyclic intermediate germacrene A; further cyclization and methyl transfer converts the intermediate into aristolochene. While in some species germacrene A remains as an enzyme-bound intermediate, it has been shown to be a minor product of the reaction in Penicillium roqueforti [5] (see also EC 4.2.3.23, germacrene-A synthase). The enzyme from Penicillium roqueforti requires Mg2+. Mn2+ can partially substitute, at low concentrations. Aristolochene is the likely parent compound for a number of sesquiterpenes produced by filamentous fungi.
Links to other databases: BRENDA, EXPASY, KEGG, Metacyc, PDB, CAS registry number: 94185-89-4
References:
1. Cane, D.E., Prabhakaran, P.C., Oliver, J.S. and McIlwaine, D.B. Aristolochene biosynthesis. Stereochemistry of the deprotonation steps in the enzymatic cyclization of farnesyl pyrophosphate. J. Am. Chem. Soc. 112 (1990) 3209-3210.
2. Cane, D.E., Prabhakaran, P.C., Salaski, E.J., Harrison, P.M.H., Noguchi, H. and Rawlings, B.J. Aristolochene biosynthesis and enzymatic cyclization of farnesyl pyrophosphate. J. Am. Chem. Soc. 111 (1989) 8914-8916.
3. Hohn, T.M. and Plattner, R.D. Purification and characterization of the sesquiterpene cyclase aristolochene synthase from Penicillium roqueforti. Arch. Biochem. Biophys. 272 (1989) 137-143. [PMID: 2544140]
4. Proctor, R.H. and Hohn, T.M. Aristolochene synthase. Isolation, characterization, and bacterial expression of a sesquiterpenoid biosynthetic gene (Ari1) from Penicillium roqueforti. J. Biol. Chem. 268 (1993) 4543-4548. [PMID: 8440737]
5. Calvert, M.J., Ashton, P.R. and Allemann, R.K. Germacrene A is a product of the aristolochene synthase-mediated conversion of farnesylpyrophosphate to aristolochene. J. Am. Chem. Soc. 124 (2002) 11636-11641. [PMID: 12296728]