EC |
2.5.1.28 |
Accepted name: |
dimethylallylcistransferase |
Reaction: |
prenyl diphosphate + 3-methyl-but-3-en-1-yl diphosphate = diphosphate + neryl diphosphate |
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For diagram of all-cis-polyprenyl diphosphate, click here |
Glossary: |
neryl = (2Z)-3,7-dimethylocta-2,6-dien-1-yl
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Other name(s): |
neryl-diphosphate synthase; dimethylallyl-diphosphate:isopentenyl-diphosphate dimethylallylcistransferase |
Systematic name: |
prenyl-diphosphate:3-methyl-but-3-en-1-yl-diphosphate prenylcistransferase |
Comments: |
This enzyme will not use larger prenyl diphosphates as efficient donors. |
Links to other databases: |
BRENDA, EXPASY, KEGG, MetaCyc, PDB, CAS registry number: 9032-79-5 |
References: |
1. |
Banthorpe, D.V., Bucknall, G.A., Doonan, H.J., Doonan, S. and Rowan, M.G. Biosynthesis of geraniol and nerol in cell-free extracts of Tanacetum vulgare. Phytochemistry 15 (1976) 91–100. |
2. |
Beytía, E., Valenzuela, P. and Cori, O. Terpene biosynthesis: formation of nerol, geraniol, and other prenols by an enzyme system from Pinus radiata seedlings. Arch. Biochem. Biophys. 129 (1969) 346–356. [DOI] [PMID: 4303098] |
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[EC 2.5.1.28 created 1984] |
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EC |
2.5.1.68 |
Accepted name: |
(2Z,6E)-farnesyl diphosphate synthase |
Reaction: |
geranyl diphosphate + isopentenyl diphosphate = diphosphate + (2Z,6E)-farnesyl diphosphate |
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For diagram of trans-polycis-polyprenol diphosphate biosynthesis, click here |
Other name(s): |
(Z)-farnesyl diphosphate synthase; Z-farnesyl diphosphate synthase |
Systematic name: |
geranyl-diphosphate:isopentenyl-diphosphate geranylcistransferase |
Comments: |
Requires Mg2+ or Mn2+ for activity. The product of this reaction is an intermediate in the synthesis of decaprenyl phosphate, which plays a central role in the biosynthesis of most features of the mycobacterial cell wall, including peptidoglycan, linker unit galactan and arabinan. Neryl diphosphate can also act as substrate. |
Links to other databases: |
BRENDA, EXPASY, KEGG, MetaCyc, PDB |
References: |
1. |
Schulbach, M.C., Mahapatra, S., Macchia, M., Barontini, S., Papi, C., Minutolo, F., Bertini, S., Brennan, P.J. and Crick, D.C. Purification, enzymatic characterization, and inhibition of the Z-farnesyl diphosphate synthase from Mycobacterium tuberculosis. J. Biol. Chem. 276 (2001) 11624–11630. [DOI] [PMID: 11152452] |
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[EC 2.5.1.68 created 2007, modified 2010] |
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EC |
2.5.1.92 |
Accepted name: |
(2Z,6Z)-farnesyl diphosphate synthase |
Reaction: |
prenyl diphosphate + 2 isopentenyl diphosphate = 2 diphosphate + (2Z,6Z)-farnesyl diphosphate (1a) prenyl diphosphate + isopentenyl diphosphate = diphosphate + neryl diphosphate (1b) neryl diphosphate + isopentenyl diphosphate = diphosphate + (2Z,6Z)-farnesyl diphosphate |
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For diagram of all-cis-polyprenyl diphosphate, click here |
Glossary: |
prenyl diphosphate = dimethylallyl diphosphate |
Other name(s): |
cis,cis-farnesyl diphosphate synthase; Z,Z-FPP synthase; zFPS; Z,Z-farnesyl pyrophosphate synthase; dimethylallyl-diphosphate:isopentenyl-diphosphate cistransferase (adding 2 isopentenyl units) |
Systematic name: |
prenyl-diphosphate:isopentenyl-diphosphate cistransferase (adding 2 isopentenyl units) |
Comments: |
This enzyme, originally characterized from wild tomato, specifically forms (2Z,6Z)-farnesyl diphosphate via neryl diphosphate and isopentenyl diphosphate. In wild tomato it is involved in the biosynthesis of several sesquiterpenes. See also EC 2.5.1.68 [(2Z,6E)-farnesyl diphosphate synthase] and EC 2.5.1.10 [(2E,6E)-farnesyl diphosphate synthase]. |
Links to other databases: |
BRENDA, EXPASY, KEGG, MetaCyc, PDB |
References: |
1. |
Sallaud, C., Rontein, D., Onillon, S., Jabes, F., Duffe, P., Giacalone, C., Thoraval, S., Escoffier, C., Herbette, G., Leonhardt, N., Causse, M. and Tissier, A. A novel pathway for sesquiterpene biosynthesis from Z,Z-farnesyl pyrophosphate in the wild tomato Solanum habrochaites. Plant Cell 21 (2009) 301–317. [DOI] [PMID: 19155349] |
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[EC 2.5.1.92 created 2010, modified 2011] |
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EC |
2.5.1.102 |
Accepted name: |
geranyl-pyrophosphate—olivetolic acid geranyltransferase |
Reaction: |
geranyl diphosphate + 2,4-dihydroxy-6-pentylbenzoate = diphosphate + cannabigerolate |
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For diagram of cannabinoid biosynthesis, click here |
Glossary: |
2,4-dihydroxy-6-pentylbenzoate = olivetolate
cannabigerolate = CBGA = 3-[(2E)-3,7-dimethylocta-2,6-dien-1-yl]-2,4-dihydroxy-6-pentylbenzoate
cannabinerolate = 3-[(2Z)-3,7-dimethylocta-2,6-dien-1-yl]-2,4-dihydroxy-6-pentylbenzoate
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Other name(s): |
GOT (ambiguous) |
Systematic name: |
geranyl-diphosphate:olivetolate geranyltransferase |
Comments: |
Part of the cannabinoids biosynthetic pathway of the plant Cannabis sativa. The enzyme can also use neryl diphosphate as substrate, forming cannabinerolate. |
Links to other databases: |
BRENDA, EXPASY, KEGG, MetaCyc |
References: |
1. |
Fellermeier, M. and Zenk, M.H. Prenylation of olivetolate by a hemp transferase yields cannabigerolic acid, the precursor of tetrahydrocannabinol. FEBS Lett. 427 (1998) 283–285. [DOI] [PMID: 9607329] |
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[EC 2.5.1.102 created 2012] |
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EC |
2.5.1.142 |
Accepted name: |
nerylneryl diphosphate synthase |
Reaction: |
prenyl diphosphate + 3 (3-methylbut-3-en-1-yl diphosphate) = 3 diphosphate + nerylneryl diphosphate (1a) prenyl diphosphate + 3-methylbut-3-en-1-yl diphosphate = diphosphate + neryl diphosphate (1b) neryl diphosphate + 3-methylbut-3-en-1-yl diphosphate = diphosphate + (2Z,6Z)-farnesyl diphosphate (1c) (2Z,6Z)-farnesyl diphosphate + 3-methylbut-3-en-1-yl diphosphate = diphosphate + nerylneryl diphosphate |
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For diagram of all-cis-polyprenyl diphosphate, click here |
Glossary: |
nerylneryl diphosphate = all-cis-tetraprenyl diphosphate |
Other name(s): |
CPT2; dimethylallyl-diphosphate:isopentenyl-diphosphate cistransferase (adding 3 isopentenyl units) |
Systematic name: |
prenyl-diphosphate:3-methylbut-3-en-1-yl-diphosphate cistransferase (adding 3 units of 3-methylbut-3-en-1-yl) |
Comments: |
Isolated from the plant Solanum lycopersicum (tomato). |
Links to other databases: |
BRENDA, EXPASY, KEGG, MetaCyc |
References: |
1. |
Akhtar, T.A., Matsuba, Y., Schauvinhold, I., Yu, G., Lees, H.A., Klein, S.E. and Pichersky, E. The tomato cis-prenyltransferase gene family. Plant J. 73 (2013) 640–652. [DOI] [PMID: 23134568] |
2. |
Matsuba, Y., Zi, J., Jones, A.D., Peters, R.J. and Pichersky, E. Biosynthesis of the diterpenoid lycosantalonol via nerylneryl diphosphate in Solanum lycopersicum. PLoS One 10:e0119302 (2015). [DOI] [PMID: 25786135] |
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[EC 2.5.1.142 created 2017] |
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EC |
3.1.7.11 |
Accepted name: |
geranyl diphosphate diphosphatase |
Reaction: |
geranyl diphosphate + H2O = geraniol + diphosphate |
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For diagram of acyclic monoterpenoid biosynthesis, click here |
Other name(s): |
geraniol synthase; geranyl pyrophosphate pyrophosphatase; GES; CtGES |
Systematic name: |
geranyl-diphosphate diphosphohydrolase |
Comments: |
Isolated from Ocimum basilicum (basil) and Cinnamomum tenuipile (camphor tree). Requires Mg2+ or Mn2+. Geraniol is labelled when formed in the presence of [18O]H2O. Thus mechanism involves a geranyl cation [1]. Neryl diphosphate is hydrolysed more slowly. May be the same as EC 3.1.7.3 monoterpenyl-diphosphatase. |
Links to other databases: |
BRENDA, EXPASY, KEGG, MetaCyc |
References: |
1. |
Iijima, Y., Gang, D.R., Fridman, E., Lewinsohn, E. and Pichersky, E. Characterization of geraniol synthase from the peltate glands of sweet basil. Plant Physiol. 134 (2004) 370–379. [DOI] [PMID: 14657409] |
2. |
Yang, T., Li, J., Wang, H.X. and Zeng, Y. A geraniol-synthase gene from Cinnamomum tenuipilum. Phytochemistry 66 (2005) 285–293. [DOI] [PMID: 15680985] |
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[EC 3.1.7.11 created 2012] |
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EC |
3.1.7.13 |
Accepted name: |
neryl diphosphate diphosphatase |
Reaction: |
neryl diphosphate + H2O = nerol + diphosphate |
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For diagram of all-cis-polyprenyl diphosphate, click here |
Glossary: |
nerol = (2Z)-3,7-dimethylocta-2,6-dien-1-ol |
Other name(s): |
NES (gene name); nerol synthase |
Systematic name: |
neryl-diphosphate diphosphohydrolase |
Comments: |
The enzyme, characterized from Glycine max (soybeans), is specific for neryl diphosphate. |
Links to other databases: |
BRENDA, EXPASY, KEGG, MetaCyc |
References: |
1. |
Zhang, M., Liu, J., Li, K. and Yu, D. Identification and characterization of a novel monoterpene synthase from soybean restricted to neryl diphosphate precursor. PLoS One 8:e75972 (2013). [DOI] [PMID: 24124526] |
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[EC 3.1.7.13 created 2020 as EC 3.7.1.27, transferred 2021 to EC 3.1.7.13] |
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EC
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3.7.1.27
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Transferred entry: | neryl diphosphate diphosphatase. Now EC 3.1.7.13, neryl diphosphate diphosphatase.
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[EC 3.7.1.27 created 2020, deleted 2021] |
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EC |
4.2.3.51 |
Accepted name: |
β-phellandrene synthase (neryl-diphosphate-cyclizing) |
Reaction: |
neryl diphosphate = β-phellandrene + diphosphate |
Other name(s): |
phellandrene synthase 1; PHS1; monoterpene synthase PHS1 |
Systematic name: |
neryl-diphosphate diphosphate-lyase [cyclizing; β-phellandrene-forming] |
Comments: |
The enzyme from Solanum lycopersicum has very poor affinity with geranyl diphosphate as substrate. Catalyses the formation of the acyclic myrcene and ocimene as major products in addition to β-phellandrene [1]. |
Links to other databases: |
BRENDA, EXPASY, KEGG, MetaCyc |
References: |
1. |
Schilmiller, A.L., Schauvinhold, I., Larson, M., Xu, R., Charbonneau, A.L., Schmidt, A., Wilkerson, C., Last, R.L. and Pichersky, E. Monoterpenes in the glandular trichomes of tomato are synthesized from a neryl diphosphate precursor rather than geranyl diphosphate. Proc. Natl. Acad. Sci. USA 106 (2009) 10865–10870. [DOI] [PMID: 19487664] |
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[EC 4.2.3.51 created 2010] |
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EC |
5.5.1.8 |
Accepted name: |
(+)-bornyl diphosphate synthase |
Reaction: |
geranyl diphosphate = (+)-bornyl diphosphate |
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For diagram of bornane and related monoterpenoids, click here |
Glossary: |
(+)-bornyl diphosphate = (1R,2S,4R)-1,7,7-trimethylbicyclo[2.2.1]heptan-2-yl diphosphate |
Other name(s): |
bornyl pyrophosphate synthase (ambiguous); bornyl pyrophosphate synthetase (ambiguous); (+)-bornylpyrophosphate cyclase; geranyl-diphosphate cyclase (ambiguous); (+)-bornyl-diphosphate lyase (decyclizing) |
Systematic name: |
(+)-bornyl-diphosphate lyase (ring-opening) |
Comments: |
Requires Mg2+. The enzyme from Salvia officinalis (sage) can also use (3R)-linalyl diphosphate or more slowly neryl diphosphate in vitro [3]. The reaction proceeds via isomeration of geranyl diphosphate to (3R)-linalyl diphosphate. The oxygen and phosphorus originally linked to C-1 of geranyl diphosphate end up linked to C-2 of (+)-bornyl diphosphate [3]. cf. EC 5.5.1.22 [(–)-bornyl diphosphate synthase]. |
Links to other databases: |
BRENDA, EXPASY, KEGG, MetaCyc, PDB, CAS registry number: 72668-91-8 |
References: |
1. |
Croteau, R. and Karp, F. Biosynthesis of monoterpenes: preliminary characterization of bornyl pyrophosphate synthetase from sage (Salvia officinalis) and demonstration that geranyl pyrophosphate is the preferred substrate for cyclization. Arch. Biochem. Biophys. 198 (1979) 512–522. [DOI] [PMID: 42356] |
2. |
Croteau, R., Gershenzon, J., Wheeler, C.J. and Satterwhite, D.M. Biosynthesis of monoterpenes: stereochemistry of the coupled isomerization and cyclization of geranyl pyrophosphate to camphane and isocamphane monoterpenes. Arch. Biochem. Biophys. 277 (1990) 374–381. [DOI] [PMID: 2178556] |
3. |
Croteau, R., Satterwhite, D.M., Cane, D.E. and Chang, C.C. Biosynthesis of monoterpenes. Enantioselectivity in the enzymatic cyclization of (+)- and (-)-linalyl pyrophosphate to (+)- and (-)-bornyl pyrophosphate. J. Biol. Chem. 261 (1986) 13438–13445. [PMID: 3759972] |
4. |
Croteau, R., Felton, N.M. and Wheeler, C.J. Stereochemistry at C-1 of geranyl pyrophosphate and neryl pyrophosphate in the cyclization to (+)- and (-)-bornyl pyrophosphate. J. Biol. Chem. 260 (1985) 5956–5962. [PMID: 3997807] |
5. |
Croteau, R.B., Shaskus, J.J., Renstrom, B., Felton, N.M., Cane, D.E., Saito, A. and Chang, C. Mechanism of the pyrophosphate migration in the enzymatic cyclization of geranyl and linalyl pyrophosphates to (+)- and (-)-bornyl pyrophosphates. Biochemistry 24 (1985) 7077–7085. [PMID: 4084562] |
6. |
McGeady, P. and Croteau, R. Isolation and characterization of an active-site peptide from a monoterpene cyclase labeled with a mechanism-based inhibitor. Arch. Biochem. Biophys. 317 (1995) 149–155. [DOI] [PMID: 7872777] |
7. |
Wise, M.L., Savage, T.J., Katahira, E. and Croteau, R. Monoterpene synthases from common sage (Salvia officinalis). cDNA isolation, characterization, and functional expression of (+)-sabinene synthase, 1,8-cineole synthase, and (+)-bornyl diphosphate synthase. J. Biol. Chem. 273 (1998) 14891–14899. [DOI] [PMID: 9614092] |
8. |
Whittington, D.A., Wise, M.L., Urbansky, M., Coates, R.M., Croteau, R.B. and Christianson, D.W. Bornyl diphosphate synthase: structure and strategy for carbocation manipulation by a terpenoid cyclase. Proc. Natl. Acad. Sci. USA 99 (2002) 15375–15380. [DOI] [PMID: 12432096] |
9. |
Peters, R.J. and Croteau, R.B. Alternative termination chemistries utilized by monoterpene cyclases: chimeric analysis of bornyl diphosphate, 1,8-cineole, and sabinene synthases. Arch. Biochem. Biophys. 417 (2003) 203–211. [DOI] [PMID: 12941302] |
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[EC 5.5.1.8 created 1984, modified 2012] |
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EC |
5.5.1.22 |
Accepted name: |
(–)-bornyl diphosphate synthase |
Reaction: |
geranyl diphosphate = (–)-bornyl diphosphate |
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For diagram of bornane and related monoterpenoids, click here |
Glossary: |
(–)-bornyl diphosphate = (2R,4S)-1,7,7-trimethylbicyclo[2.2.1]hept-2-yl diphosphate |
Other name(s): |
bornyl pyrophosphate synthase (ambiguous); bornyl pyrophosphate synthetase (ambiguous); (–)-bornyl pyrophosphate cyclase; bornyl diphosphate synthase; geranyl-diphosphate cyclase (ambiguous); (–)-bornyl-diphosphate lyase (decyclizing) |
Systematic name: |
(–)-bornyl-diphosphate lyase (ring-opening) |
Comments: |
Requires Mg2+. The enzyme from Tanacetum vulgare (tansy) can also use (3S)-linalyl diphosphate or more slowly neryl diphosphate in vitro. The reaction proceeds via isomeration of geranyl diphosphate to (3S)-linalyl diphosphate [3]. The oxygen and phosphorus originally linked to C-1 of geranyl diphosphate end up linked to C-2 of (–)-bornyl diphosphate [4]. cf. EC 5.5.1.8 (+)-bornyl diphosphate synthase. |
Links to other databases: |
BRENDA, EXPASY, KEGG, MetaCyc, CAS registry number: 110639-17-3 |
References: |
1. |
Croteau, R., Gershenzon, J., Wheeler, C.J. and Satterwhite, D.M. Biosynthesis of monoterpenes: stereochemistry of the coupled isomerization and cyclization of geranyl pyrophosphate to camphane and isocamphane monoterpenes. Arch. Biochem. Biophys. 277 (1990) 374–381. [DOI] [PMID: 2178556] |
2. |
Croteau, R. and Shaskus, J. Biosynthesis of monoterpenes: demonstration of a geranyl pyrophosphate:(-)-bornyl pyrophosphate cyclase in soluble enzyme preparations from tansy (Tanacetum vulgare). Arch. Biochem. Biophys. 236 (1985) 535–543. [DOI] [PMID: 3970524] |
3. |
Croteau, R., Felton, N.M. and Wheeler, C.J. Stereochemistry at C-1 of geranyl pyrophosphate and neryl pyrophosphate in the cyclization to (+)- and (-)-bornyl pyrophosphate. J. Biol. Chem. 260 (1985) 5956–5962. [PMID: 3997807] |
4. |
Croteau, R.B., Shaskus, J.J., Renstrom, B., Felton, N.M., Cane, D.E., Saito, A. and Chang, C. Mechanism of the pyrophosphate migration in the enzymatic cyclization of geranyl and linalyl pyrophosphates to (+)- and (-)-bornyl pyrophosphates. Biochemistry 24 (1985) 7077–7085. [PMID: 4084562] |
5. |
Adam, K.P. and Croteau, R. Monoterpene biosynthesis in the liverwort Conocephalum conicum: demonstration of sabinene synthase and bornyl diphosphate synthase. Phytochemistry 49 (1998) 475–480. [DOI] [PMID: 9747540] |
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[EC 5.5.1.22 created 2012] |
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