Reaction: (2E,6E)-farnesyl diphosphate = pentalenene + diphosphate
For reaction pathway click here and mechanism click here.
Glossary: pentalenene = (1R,8aR)-1,4,7,7-tetramethyl-1,2,3,3a,5a,6,7,8-octahydrocyclopenta[c]pentalene
Other name(s): pentalenene synthetase; 2-trans,6-trans-farnesyl-diphosphate diphosphate-lyase (cyclizing, pentalenene-forming)
Systematic name: (2E,6E)-farnesyl-diphosphate diphosphate-lyase (cyclizing, pentalenene-forming)
Comments: Isolated from Streptomyces avermitilis. The enzyme is involved in the biosynthesis of pentalenolactone and related antibiotics. The 9si hydrogen of farnesyl diphosphate undergoes a 1,2-hydride shift where it becomes the 1α hydrogen of pentalenene.
Links to other databases: BRENDA, EXPASY, KEGG, Metacyc, PDB, CAS registry number: 90597-46-9
References:
1. Cane, D.E. Cell-free studies of monoterpene and sesquiterpene biosynthesis. Biochem. Soc. Trans. 11 (1983) 510-515. [PMID: 6642060]
2. Cane, D.E. and Tillman, A.M. Pentalenene biosynthesis and the enzymic cyclization of farnesyl pyrophosphate. J. Am. Chem. Soc. 105 (1983) 122-124.
3. Cane, D.E., Sohng, J.K., Lamberson, C.R., Rudnicki, S.M., Wu, Z., Lloyd, M.D., Oliver, J.S. and Hubbard, B.R. Pentalenene synthase. Purification, molecular cloning, sequencing, and high-level expression in Escherichia coli of a terpenoid cyclase from Streptomyces UC5319. Biochemistry 33 (1994) 5846-5857. [PMID: 8180213]
4. Cane, D.E., Abell, C., Harrison, P.H., Hubbard, B.R., Kane, C.T., Lattman, R., Oliver, J.S. and Weiner, S.W. Terpenoid biosynthesis and the stereochemistry of enzyme-catalysed allylic addition-elimination reactions. Philos. Trans. R. Soc. Lond. B Biol. Sci. 332 (1991) 123-129. [PMID: 1678531]
5. Lesburg, C.A., Zhai, G., Cane, D.E. and Christianson, D.W. Crystal structure of pentalenene synthase: mechanistic insights on terpenoid cyclization reactions in biology. Science 277 (1997) 1820-1824. [PMID: 9295272]
6. Zu, L., Xu, M., Lodewyk, M.W., Cane, D.E., Peters, R.J. and Tantillo, D.J. Effect of isotopically sensitive branching on product distribution for pentalenene synthase: support for a mechanism predicted by quantum chemistry. J. Am. Chem. Soc. 134 (2012) 11369-11371. [PMID: 22738258]