Continued from EC 4.2.2 to EC 4.2.3.1-50
EC 4.2.3 Acting on Phosphates
EC 4.2.99 Other Carbon-Oxygen Lyases
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, CAS registry number:
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. [PMID: 19487664]
Accepted name: (4S)-β-phellandrene synthase (geranyl-diphosphate-cyclizing)
Reaction: geranyl diphosphate = (4S)-β-phellandrene + diphosphate
For diagram click here.
Other name(s): phellandrene synthase; (–)-β-phellandrene synthase; (–)-(4S)-β-phellandrene synthase
Systematic name: geranyl-diphosphate diphosphate-lyase [cyclizing; (4S)-β-phellandrene-forming)
Comments: Requires Mn2+. Mg2+ is not effective [1]. Some (–)-α-phellandrene is also formed [3]. The reaction involves a 1,3-hydride shift [4].
Links to other databases: BRENDA, EXPASY, KEGG, CAS registry number:
References:
1. Savage, T.J., Hatch, M.W. and Croteau, R. Monoterpene synthases of Pinus contorta and related conifers. A new class of terpenoid cyclase. J. Biol. Chem. 269 (1994) 4012-4020. [PMID: 8307957]
2. Bohlmann, J., Phillips, M., Ramachandiran, V., Katoh, S. and Croteau, R. cDNA cloning, characterization, and functional expression of four new monoterpene synthase members of the Tpsd gene family from grand fir (Abies grandis). Arch. Biochem. Biophys. 368 (1999) 232-243. [PMID: 10441373]
3. Wagschal, K., Savage, T.J. and Croteau, R. Isotopically sensitive branching as a tool for evaluating multiple product formation by monoterpene cyclases. Tetrahedron 31 (1991) 5933-5944.
4. LaFever, R.E. and Croteau, R. Hydride shifts in the biosynthesis of the p-menthane monoterpenes α-terpinene, γ-terpinene, and β-phellandrene. Arch. Biochem. Biophys. 301 (1993) 361-366. [PMID: 8460944]
Accepted name: (+)-endo-β-bergamotene synthase [(2Z,6Z)-farnesyl diphosphate cyclizing]
Reaction: (2Z,6Z)-farnesyl diphosphate = (+)-endo-β-bergamotene + diphosphate
For diagram of reaction click here.
Other name(s): SBS
Systematic name: (2Z,6Z)-farnesyl diphosphate lyase (cyclizing; (+)-endo-β-bergamotene-forming)
Comments: The enzyme synthesizes a mixture of sesquiterpenoids from (2Z,6Z)-farnesyl diphosphate. Following dephosphorylation of (2Z,6Z)-farnesyl diphosphate, the (2Z,6Z)-farnesyl carbocation is converted to either the (6R)- or the (6S)-bisabolyl cations depending on the stereochemistry of the 6,1 closure. The (6R)-bisabolyl cation will then lead to the formation of (+)-α-santalene (see EC 4.2.3.50), while the (6S)-bisabolyl cation will give rise to (–)-endo-α-bergamotene (see EC 4.2.3.54), as well as (+)-endo-β-bergamotene. Small amounts of (–)-epi-β-santalene are also formed from the (6R)-bisabolyl cation and small amounts of (–)-exo-α-bergamotene are formed from the (6S)-bisabolyl cation [1].
Links to other databases: BRENDA, EXPASY, KEGG, CAS registry number:
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. [PMID: 19155349]
Accepted name: (–)-endo-α-bergamotene synthase [(2Z,6Z)-farnesyl diphosphate cyclizing]
Reaction: (2Z,6Z)-farnesyl diphosphate = (–)-endo-α-bergamotene + diphosphate
For diagram of reaction click here.
Other name(s): SBS
Systematic name: (2Z,6Z)-farnesyl diphosphate lyase (cyclizing; (–)-endo-α-bergamotene-forming)
Comments: The enzyme synthesizes a mixture of sesquiterpenoids from (2Z,6Z)-farnesyl diphosphate. Following dephosphorylation of (2Z,6Z)-farnesyl diphosphate, the (2Z,6Z)-farnesyl carbocation is converted to either the (6R)- or the (6S)-bisabolyl cations depending on the stereochemistry of the 6,1 closure. The (6R)-bisabolyl cation will then lead to the formation of (+)-α-santalene (see EC 4.2.3.50), while the (6S)-bisabolyl cation will give rise to (+)-endo-β-bergamotene (EC 4.2.3.53) as well as (–)-endo-α-bergamotene. Small amounts of (–)-epi-β-santalene are also formed from the (6R)-bisabolyl cation and small amounts of (–)-exo-α-bergamotene are formed from the (6S)-bisabolyl cation [1].
Links to other databases: BRENDA, EXPASY, KEGG, CAS registry number:
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. [PMID: 19155349]
Accepted name: (S)-β-bisabolene synthase
Reaction: (2E,6E)-farnesyl diphosphate = (S)-β-bisabolene + diphosphate
For diagram of reaction click here and mechanism click here.
Systematic name: (2E,6E)-farnesyl-diphosphate diphosphate-lyase [(S)-β-bisabolene-forming]
Links to other databases: BRENDA, EXPASY, KEGG, CAS registry number:
References:
1. Fujisawa, M., Harada, H., Kenmoku, H., Mizutani, S. and Misawa, N. Cloning and characterization of a novel gene that encodes (S)-β-bisabolene synthase from ginger, Zingiber officinale. Planta 232 (2010) 121-130. [PMID: 20229191]
Accepted name: γ-humulene synthase
Reaction: (2E,6E)-farnesyl diphosphate = γ-humulene + diphosphate
For diagram of reaction click here.
Other name(s): humulene cyclase
Systematic name: (2E,6E)-farnesyl-diphosphate diphosphate-lyase (γ-humulene-forming)
Links to other databases: BRENDA, EXPASY, KEGG, CAS registry number:
References:
1. Steele, C.L., Crock, J., Bohlmann, J. and Croteau, R. Sesquiterpene synthases from grand fir (Abies grandis). Comparison of constitutive and wound-induced activities, and cDNA isolation, characterization, and bacterial expression of δ-selinene synthase and γ-humulene synthase. J. Biol. Chem. 273 (1998) 2078-2089. [PMID: 9442047]
2. Little, D.B. and Croteau, R.B. Alteration of product formation by directed mutagenesis and truncation of the multiple-product sesquiterpene synthases δ-selinene synthase and γ-humulene synthase. Arch. Biochem. Biophys. 402 (2002) 120-135. [PMID: 12051690]
Accepted name: (–)-β-caryophyllene synthase
Reaction: (2E,6E)-farnesyl diphosphate = (–)-β-caryophyllene + diphosphate
For diagram of reaction click here.
Other name(s): β-caryophyllene synthase; (2E,6E)-farnesyl-diphosphate diphosphate-lyase (caryophyllene-forming)
Systematic name: (2E,6E)-farnesyl-diphosphate diphosphate-lyase [(–)-caryophyllene-forming]
Comments: Widely distributed in higher plants, cf. EC 4.2.3.89 (+)-β-caryophyllene synthase.
Links to other databases: BRENDA, EXPASY, KEGG, CAS registry number: 110639-18-4
References:
1. Cai, Y., Jia, J.W., Crock, J., Lin, Z.X., Chen, X.Y. and Croteau, R. A cDNA clone for β-caryophyllene synthase from Artemisia annua. Phytochemistry 61 (2002) 523-529. [PMID: 12409018]
Accepted name: longifolene synthase
Reaction: (2E,6E)-farnesyl diphosphate = longifolene + diphosphate
For diagram of reaction click here and mechanism click here.
Systematic name: (2E,6E)-farnesyl-diphosphate diphosphate-lyase (longifolene-forming)
Comments: A well as 61% longifolene the enzyme gives 15% of α-longipinene, 6% longicyclene and traces of other sesquiterpenoids.
Links to other databases: BRENDA, EXPASY, KEGG, CAS registry number:
References:
1. Martin, D.M., Faldt, J. and Bohlmann, J. Functional characterization of nine Norway Spruce TPS genes and evolution of gymnosperm terpene synthases of the TPS-d subfamily. Plant Physiol. 135 (2004) 1908-1927. [PMID: 15310829]
Accepted name: (E)-γ-bisabolene synthase
Reaction: (2E,6E)-farnesyl diphosphate = (E)-γ-bisabolene + diphosphate
For diagram of reaction click here.
Systematic name: (2E,6E)-farnesyl-diphosphate diphosphate-lyase [(E)-γ-bisabolene-forming]
References:
1. Huber, D.P.W., Philippe, R.N., Godard, K.-A., Sturrock, R.N. and Bohlmann, J. Characterization of four terpene synthase cDNAs from methyl jasmonate-induced Douglas-fir, Pseudotsuga menziesii. Phytochemistry 66 (2005) 1427-1439. [PMID: 15921711]
Accepted name: germacrene C synthase
Reaction: (2E,6E)-farnesyl diphosphate = germacrene C + diphosphate
For diagram of reaction click here.
Systematic name: (2E,6E)-farnesyl-diphosphate diphosphate-lyase (germacrene-C-forming)
Links to other databases: BRENDA, EXPASY, KEGG, CAS registry number:
References:
1. Colby, S.M., Crock, J., Dowdle-Rizzo, B., Lemaux, P.G. and Croteau, R. Germacrene C synthase from Lycopersicon esculentum cv. VFNT cherry tomato: cDNA isolation, characterization, and bacterial expression of the multiple product sesquiterpene cyclase. Proc. Natl. Acad. Sci. USA 95 (1998) 2216-2221. [PMID: 9482865]
Accepted name: 5-epiaristolochene synthase
Reaction: (2E,6E)-farnesyl diphosphate = (+)-5-epiaristolochene + diphosphate
For diagram of reaction click here.
Other name(s): 5-epi-aristolochene synthase; tobacco epiaristolochene synthase; farnesyl pyrophosphate cyclase (ambiguous); EAS; TEAS
Systematic name: (2E,6E)-farnesyl-diphosphate diphosphate-lyase [(+)-5-epiaristolochene-forming]
Comments: Initial cyclization gives (+)-germacrene A in an enzyme bound form which is not released to the medium.
Links to other databases: BRENDA, EXPASY, KEGG, CAS registry number:
References:
1. Back, K., Yin, S. and Chappell, J. Expression of a plant sesquiterpene cyclase gene in Escherichia coli. Arch. Biochem. Biophys. 315 (1994) 527-532. [PMID: 7986100]
2. Starks, C.M., Back, K., Chappell, J. and Noel, J.P. Structural basis for cyclic terpene biosynthesis by tobacco 5-epi-aristolochene synthase. Science 277 (1997) 1815-1820. [PMID: 9295271]
3. Back, K., He, S., Kim, K.U. and Shin, D.H. Cloning and bacterial expression of sesquiterpene cyclase, a key branch point enzyme for the synthesis of sesquiterpenoid phytoalexin capsidiol in UV-challenged leaves of Capsicum annuum. Plant Cell Physiol. 39 (1998) 899-904. [PMID: 9816674]
4. Rising, K.A., Starks, C.M., Noel, J.P. and Chappell, J. Demonstration of germacrene A as an intermediate in 5-epi-aristolochene synthase catalysis. J. Am. Chem. Soc. 122 (2000) 1861-1866.
5. Bohlmann, J., Stauber, E.J., Krock, B., Oldham, N.J., Gershenzon, J. and Baldwin, I.T. Gene expression of 5-epi-aristolochene synthase and formation of capsidiol in roots of Nicotiana attenuata and N. sylvestris. Phytochemistry 60 (2002) 109-116. [PMID: 12009313]
6. O'Maille, P.E., Chappell, J. and Noel, J.P. Biosynthetic potential of sesquiterpene synthases: alternative products of tobacco 5-epi-aristolochene synthase. Arch. Biochem. Biophys. 448 (2006) 73-82. [PMID: 16375847]
Accepted name: (–)-γ-cadinene synthase [(2Z,6E)-farnesyl diphosphate cyclizing]
Reaction: (2Z,6E)-farnesyl diphosphate = (–)-γ-cadinene + diphosphate
For diagram of reaction click here.
Other name(s): (–)-γ-cadinene cyclase
Systematic name: (2Z,6E)-farnesyl-diphosphate diphosphate-lyase [(–)-γ-cadinene-forming]
Comments: Isolated from the liverwort Heteroscyphus planus. cf EC 4.2.3.92 (+)-γ-cadinene synthase.
Links to other databases: BRENDA, EXPASY, KEGG, CAS registry number:
References:
1. Nabeta, K., Fujita, M., Komuro, K., Katayama, K., and Takasawa, T. In vitro biosynthesis of cadinanes by cell-free extracts of cultured cells of Heteroscyphus planus. J. Chem. Soc., Perkin Trans. 1 (1997) 2065-2070.
Accepted name: (+)-cubenene synthase
Reaction: (2E,6E)-farnesyl diphosphate = (+)-cubenene + diphosphate
For diagram of reaction click here.
Systematic name: (2E,6E)-farnesyl-diphosphate diphosphate-lyase [(+)-cubenene-forming]
Comments: Requires Mg2+.
Links to other databases: BRENDA, EXPASY, KEGG, CAS registry number:
References:
1. Nabeta, K., Kigure, K., Fujita, M., Nagoya, T., Ishikawa, T., Okuyama, H. and Takasawa, T. Bioynthesis of (+)-cubenene and (+)-epicubenol by cell-free extracts of cultured cells of Heteroscyphus planus and cyclization of [2H]farnesyl diphosphates. J. Chem. Soc., Perkin Trans. 1 (1995) 1935-1939.
2. Nabeta, K., Fujita, M., Komuro, K., Katayama, K., and Takasawa, T. In vitro biosynthesis of cadinanes by cell-free extracts of cultured cells of Heteroscyphus planus. J. Chem. Soc., Perkin Trans. 1 (1997) 2065-2070.
Accepted name: (+)-epicubenol synthase
Reaction: (2E,6E)-farnesyl diphosphate + H2O = (+)-epicubenol + diphosphate
For diagram of reaction click here.
Other name(s): farnesyl pyrophosphate cyclase (ambiguous)
Systematic name: (2E,6E)-farnesyl-diphosphate diphosphate-lyase [(+)-epicubenol-forming]
Comments: Requires Mg2+. In the bacteria Streptomyces and the liverwort Heteroscyphus the (+)-isomer is formed in contrast to higher plants where the (–)-isomer is formed.
Links to other databases: BRENDA, EXPASY, KEGG, CAS registry number:
References:
1. Cane, D.E., Tandon, M., and Prabhakaran, P.C. Epicubenol synthase and the enzymatic cyclization of farnesyl diphosphate. J. Am. Chem. Soc. 115 (1993) 8103-8106.
2. Cane, D.E. and Tandon, M. Biosynthesis of (+)-epicubenol. Tetrahedron Lett. 35 (1994) 5355-5358.
3. Cane, D.E. and Tandon, M. Epicubenol synthase and the stereochemistry of the enzymatic cyclization of farnesyl and nerolidyl diphosphate. J. Am. Chem. Soc. 117 (1995) 5602-5603.
4. Nabeta, K., Kigure, K., Fujita, M., Nagoya, T., Ishikawa, T., Okuyama, H. and Takasawa, T. Bioynthesis of (+)-cubenene and (+)-epicubenol by cell-free extracts of cultured cells of Heteroscyphus planus and cyclization of [2H]farnesyl diphosphates. J. Chem. Soc., Perkin Trans. 1 (1995) 1935-1939.
5. Nabeta, K., Fujita, M., Komuro, K., Katayama, K., and Takasawa, T. In vitro biosynthesis of cadinanes by cell-free extracts of cultured cells of Heteroscyphus planus. J. Chem. Soc., Perkin Trans. 1 (1997) 2065-2070.
Accepted name: zingiberene synthase
Reaction: (2E,6E)-farnesyl diphosphate = zingiberene + diphosphate
For diagram of reaction click here and mechanism click here.
Other name(s): α-zingiberene synthase; ZIS
Systematic name: (2E,6E)-farnesyl-diphosphate diphosphate-lyase (zingiberene-forming)
Links to other databases: BRENDA, EXPASY, KEGG, CAS registry number:
References:
1. Davidovich-Rikanati, R., Lewinsohn, E., Bar, E., Iijima, Y., Pichersky, E. and Sitrit, Y. Overexpression of the lemon basil α-zingiberene synthase gene increases both mono- and sesquiterpene contents in tomato fruit. Plant J. 56 (2008) 228-238. [PMID: 18643974]
Accepted name: β-selinene cyclase
Reaction: (2E,6E)-farnesyl diphosphate = β-selinene + diphosphate
For diagram of reaction click here.
Systematic name: (2E,6E)-farnesyl-diphosphate diphosphate-lyase (β-selinene-forming)
Comments: Initial cyclization gives (+)-germacrene A in an enzyme bound form which is not released to the medium.
Links to other databases: BRENDA, EXPASY, KEGG, CAS registry number:
References:
1. Belingher, L., Cartayrade, A., Pauly, G. and Gleizes, M. Partial purification and properties of the sesquiterpene β-selinene cyclase from Citrofortunella mitis. Plant Sci. 84 (1992) 129-136.
Accepted name: cis-muuroladiene synthase
Reaction: (1) (2E,6E)-farnesyl diphosphate = cis-muurola-3,5-diene + diphosphate
(2) (2E,6E)-farnesyl diphosphate = cis-muurola-4(14),5-diene + diphosphate
For diagram of reaction click here.
Other name(s): MxpSS1
Systematic name: (2E,6E)-farnesyl-diphosphate diphosphate-lyase (cis-muuroladiene-forming)
Comments: The recombinant enzyme from black peppermint (Mentha x piperita) gave a mixture of cis-muurola-3,5-diene (45%) and cis-muurola-4(14),5-diene (43%).
Links to other databases: BRENDA, EXPASY, KEGG, CAS registry number:
References:
1. Prosser, I.M., Adams, R.J., Beale, M.H., Hawkins, N.D., Phillips, A.L., Pickett, J.A. and Field, L.M. Cloning and functional characterisation of a cis-muuroladiene synthase from black peppermint (Mentha × piperita) and direct evidence for a chemotype unable to synthesise farnesene. Phytochemistry 67 (2006) 1564-1571. [PMID: 16083926]
Accepted name: β-eudesmol synthase
Reaction: (2E,6E)-farnesyl diphosphate + H2O = β-eudesmol + diphosphate
For diagram of rection click here and for mechanism click here
Systematic name: (2E,6E)-farnesyl-diphosphate diphosphate-lyase (β-eudesmol-forming)
Comments: The recombinant enzyme from ginger (Zingiber zerumbet) gives 62.6% β-eudesmol, 16.8% 10-epi-γ-eudesmol (cf. EC 4.2.3.84, 10-epi-γ-eudesmol synthase), 10% α-eudesmol (cf. EC 4.2.3.85, α-eudesmol synthase), and 5.6% aristolene.
Links to other databases: BRENDA, EXPASY, KEGG, CAS registry number:
References:
1. Yu, F., Harada, H., Yamasaki, K., Okamoto, S., Hirase, S., Tanaka, Y., Misawa, N. and Utsumi, R. Isolation and functional characterization of a β-eudesmol synthase, a new sesquiterpene synthase from Zingiber zerumbet Smith. FEBS Lett. 582 (2008) 565-572. [PMID: 18242187]
Accepted name: (+)-α-barbatene synthase
Reaction: (2E,6E)-farnesyl diphosphate = (+)-α-barbatene + diphosphate
For diagram of reaction click here and for mechanism click here
Other name(s): AtBS
Systematic name: (2E,6E)-farnesyl-diphosphate diphosphate-lyase [(+)-α-barbatene-forming]
Comments: The recombinant enzyme from the plant Arabidopsis thaliana produces 27.3% α-barbatene, 17.8% thujopsene (cf. EC 4.2.3.79, thujopsene synthase) and 9.9% β-chamigrene (cf. EC 4.2.3.78, β-chamigrene synthase) [1] plus traces of other sesquiterpenoids [2].
Links to other databases: BRENDA, EXPASY, KEGG, CAS registry number:
References:
1. Wu, S., Schoenbeck, M.A., Greenhagen, B.T., Takahashi, S., Lee, S., Coates, R.M. and Chappell, J. Surrogate splicing for functional analysis of sesquiterpene synthase genes. Plant Physiol. 138 (2005) 1322-1333. [PMID: 15965019]
2. Tholl, D., Chen, F., Petri, J., Gershenzon, J. and Pichersky, E. Two sesquiterpene synthases are responsible for the complex mixture of sesquiterpenes emitted from Arabidopsis flowers. Plant J. 42 (2005) 757-771. [PMID: 15918888]
Accepted name: patchoulol synthase
Reaction: (2E,6E)-farnesyl diphosphate + H2O = patchoulol + diphosphate
For diagram of reaction click here and mechanism click here.
Systematic name: (2E,6E)-farnesyl-diphosphate diphosphate-lyase (patchoulol-forming)
Links to other databases: BRENDA, EXPASY, KEGG, CAS registry number:
References:
1. Croteau, R., Munck, S.L., Akoh, C.C., Fisk, H.J. and Satterwhite, D.M. Biosynthesis of the sesquiterpene patchoulol from farnesyl pyrophosphate in leaf extracts of Pogostemon cablin (patchouli): mechanistic considerations. Arch. Biochem. Biophys. 256 (1987) 56-68. [PMID: 3038029]
2. Munck, S.L. and Croteau, R. Purification and characterization of the sesquiterpene cyclase patchoulol synthase from Pogostemon cablin. Arch. Biochem. Biophys. 282 (1990) 58-64. [PMID: 2171435]
3. Faraldos, J.A., Wu, S., Chappell, J. and Coates, R.M. Doubly deuterium-labeled patchouli alcohol from cyclization of singly labeled [2-2H1]farnesyl diphosphate catalyzed by recombinant patchoulol synthase. J. Am. Chem. Soc. 132 (2010) 2998-3008. [PMID: 20148554]
Accepted name: (E,E)-germacrene B synthase
Reaction: (2E,6E)-farnesyl diphosphate = (E,E)-germacrene B + diphosphate
For diagram of reaction click here.
Systematic name: (2E,6E)-farnesyl-diphosphate diphosphate-lyase [(E,E)-germacrene-B-forming]
Links to other databases: BRENDA, EXPASY, KEGG, CAS registry number:
References:
1. van Der Hoeven, R.S., Monforte, A.J., Breeden, D., Tanksley, S.D. and Steffens, J.C. Genetic control and evolution of sesquiterpene biosynthesis in Lycopersicon esculentum and L. hirsutum. Plant Cell 12 (2000) 2283-2294. [PMID: 11090225]
Accepted name: α-gurjunene synthase
Reaction: (2E,6E)-farnesyl diphosphate = (–)-α-gurjunene + diphosphate
For diagram of reaction click here.
Systematic name: (2E,6E)-farnesyl-diphosphate diphosphate-lyase [(–)-α-gurjunene-forming]
Comments: Initial cyclization probably gives biyclogermacrene in an enzyme bound form which is not released to the medium. The enzyme from Solidago canadensis also forms a small amount of (+)-γ-gurjunene [1].
Links to other databases: BRENDA, EXPASY, KEGG, CAS registry number:
References:
1. Schmidt, C.O., Bouwmeester, H.J., Bulow, N. and Konig, W.A. Isolation, characterization, and mechanistic studies of (–)-α-gurjunene synthase from Solidago canadensis. Arch. Biochem. Biophys. 364 (1999) 167-177. [PMID: 10190971]
Accepted name: valencene synthase
Reaction: (2E,6E)-farnesyl diphosphate = (+)-valencene + diphosphate
For diagram of reaction click here.
Systematic name: (2E,6E)-farnesyl-diphosphate diphosphate-lyase (valencene-forming)
Comments: The recombinant enzyme from Vitis vinifera gave 49.5% (+)-valencene and 35.5% (–)-7-epi-α-selinene. Initial cyclization gives (+)-germacrene A in an enzyme bound form which is not released to the medium.
Links to other databases: BRENDA, EXPASY, KEGG, CAS registry number:
References:
1. Lucker, J., Bowen, P. and Bohlmann, J. Vitis vinifera terpenoid cyclases: functional identification of two sesquiterpene synthase cDNAs encoding (+)-valencene synthase and (–)-germacrene D synthase and expression of mono- and sesquiterpene synthases in grapevine flowers and berries. Phytochemistry 65 (2004) 2649-2659. [PMID: 15464152]
Accepted name: presilphiperfolanol synthase
Reaction: (2E,6E)-farnesyl diphosphate + H2O = presilphiperfolan-8β-ol + diphosphate
For diagram of reaction click here and mechanism click here.
Other name(s): BcBOT2, CND15
Systematic name: (2E,6E)-farnesyl-diphosphate diphosphohydrolase (presilphiperfolan-8β-ol-forming)
Comments: Requires Mg2+. Presilphiperfolan-8β-ol is the precursor of botrydial, a phytotoxic sesquiterpene metabolite secreted by the fungus Botryotinia fuckeliana (Botrytis cinerea), the causal agent of gray mold disease in plants.
Links to other databases: BRENDA, EXPASY, KEGG, CAS registry number:
References:
1. Pinedo, C., Wang, C.M., Pradier, J.M., Dalmais, B., Choquer, M., Le Pecheur, P., Morgant, G., Collado, I.G., Cane, D.E. and Viaud, M. Sesquiterpene synthase from the botrydial biosynthetic gene cluster of the phytopathogen Botrytis cinerea. ACS Chem Biol 3 (2008) 791-801. [PMID: 19035644]
2. Wang, C.M., Hopson, R., Lin, X. and Cane, D.E. Biosynthesis of the sesquiterpene botrydial in Botrytis cinerea. Mechanism and stereochemistry of the enzymatic formation of presilphiperfolan-8β-ol. J. Am. Chem. Soc. 131 (2009) 8360-8361. [PMID: 19476353]
Accepted name: (–)-germacrene D synthase
Reaction: (2E,6E)-farnesyl diphosphate = (–)-germacrene D + diphosphate
For diagram of reaction click here.
Glossary: (–)-germacrene D = (1E,6E,8S)-1-methyl-5-methylidene-8-(propan-2-yl)cyclodeca-1,6-diene
Systematic name: (2E,6E)-farnesyl-diphosphate diphosphate-lyase [(–)-germacrene-D-forming]
Comments: In Solidago canadensis the biosynthesis results in the pro-R hydrogen at C-1 of the farnesy diphosphate ending up at C-11 of the (–)-germacrene D [1]. With Streptomyces coelicolor the pro-S hydrogen at C-1 ends up at C-11 of the (–)-germacrene D [2].
Links to other databases: BRENDA, EXPASY, KEGG, CAS registry number:
References:
1. Schmidt, C.O., Bouwmeester, H.J., Franke, S. and König, W.A. Mechanisms of the biosynthesis of sesquiterpene enantiomers (+)- and (–)-germacrene D in Solidago canadensis. Chirality 11 (1999) 353-362.
2. He, X. and Cane, D.E. Mechanism and stereochemistry of the germacradienol/germacrene D synthase of Streptomyces coelicolor A3(2). J. Am. Chem. Soc. 126 (2004) 2678-2679. [PMID: 14995166]
3. Lucker, J., Bowen, P. and Bohlmann, J. Vitis vinifera terpenoid cyclases: functional identification of two sesquiterpene synthase cDNAs encoding (+)-valencene synthase and (–)-germacrene D synthase and expression of mono- and sesquiterpene synthases in grapevine flowers and berries. Phytochemistry 65 (2004) 2649-2659. [PMID: 15464152]
4. Prosser, I., Altug, I.G., Phillips, A.L., Konig, W.A., Bouwmeester, H.J. and Beale, M.H. Enantiospecific (+)- and (–)-germacrene D synthases, cloned from goldenrod, reveal a functionally active variant of the universal isoprenoid-biosynthesis aspartate-rich motif. Arch. Biochem. Biophys. 432 (2004) 136-144. [PMID: 15542052]
Accepted name: (+)-δ-selinene synthase
Reaction: (2E,6E)-farnesyl diphosphate = (+)-δ-selinene + diphosphate
For diagram of reaction click here.
Glossary: (+)-δ-selinene = (4aR)-1,4a-dimethyl-7-(propan-2-yl)-2,3,4,4a,5,6-hexahydronaphthalene
Systematic name: (2E,6E)-farnesyl-diphosphate diphosphate-lyase [(+)-δ-selinene-forming]
Comments: Initial cyclization gives germacrene C in an enzyme bound form which is not released to the medium.
Links to other databases: BRENDA, EXPASY, KEGG, CAS registry number:
References:
1. Steele, C.L., Crock, J., Bohlmann, J. and Croteau, R. Sesquiterpene synthases from grand fir (Abies grandis). Comparison of constitutive and wound-induced activities, and cDNA isolation, characterization, and bacterial expression of δ-selinene synthase and γ-humulene synthase. J. Biol. Chem. 273 (1998) 2078-2089. [PMID: 9442047]
2. Little, D.B. and Croteau, R.B. Alteration of product formation by directed mutagenesis and truncation of the multiple-product sesquiterpene synthases δ-selinene synthase and γ-humulene synthase. Arch. Biochem. Biophys. 402 (2002) 120-135. [PMID: 12051690]
Accepted name: (+)-germacrene D synthase
Reaction: (2E,6E)-farnesyl diphosphate = (+)-germacrene D + diphosphate
For diagram of reaction click here.
Glossary: (+)-germacrene D = (1E,6E,8R)-1-methyl-5-methylidene-8-(propan-2-yl)cyclodeca-1,6-diene
Systematic name: (2E,6E)-farnesyl-diphosphate diphosphate-lyase [(+)-germacrene-D-forming]
Comments: Requires Mg2+, Mn2+, Ni2+ or Co2+. The formation of (+)-germacrene D involves a 1,2-hydride shift whereas for (–)-germacrene D there is a 1,3-hydride shift (see EC 4.2.3.75).
Links to other databases: BRENDA, EXPASY, KEGG, CAS registry number:
References:
1. Picaud, S., Olsson, M.E., Brodelius, M. and Brodelius, P.E. Cloning, expression, purification and characterization of recombinant (+)-germacrene D synthase from Zingiber officinale. Arch. Biochem. Biophys. 452 (2006) 17-28. [PMID: 16839518]
Accepted name: β-chamigrene synthase
Reaction: (2E,6E)-farnesyl diphosphate = (+)-β-chamigrene + diphosphate
For diagram of reaction click here and mechanism click here.
Systematic name: (2E,6E)-farnesyl diphosphate lyase (cyclizing, (+)-β-chamigrene-forming)
Comments: The recombinant enzyme from the plant Arabidopsis thaliana produces 27.3% (+)-α-barbatene, 17.8% (+)-thujopsene and 9.9% (+)-β-chamigrene [1] plus traces of other sesquiterpenoids [2]. See EC 4.2.3.69 (+)-α-barbatene synthase, and EC 4.2.3.79 thujopsene synthase.
Links to other databases: BRENDA, EXPASY, KEGG, CAS registry number:
References:
1. Wu, S., Schoenbeck, M.A., Greenhagen, B.T., Takahashi, S., Lee, S., Coates, R.M. and Chappell, J. Surrogate splicing for functional analysis of sesquiterpene synthase genes. Plant Physiol. 138 (2005) 1322-1333. [PMID: 15965019]
2. Tholl, D., Chen, F., Petri, J., Gershenzon, J. and Pichersky, E. Two sesquiterpene synthases are responsible for the complex mixture of sesquiterpenes emitted from Arabidopsis flowers. Plant J. 42 (2005) 757-771. [PMID: 15918888]
Accepted name: thujopsene synthase
Reaction: (2E,6E)-farnesyl diphosphate = (+)-thujopsene + diphosphate
For diagram of reaction click here and mechanism click here.
Systematic name: (2E,6E)-farnesyl diphosphate lyase (cyclizing, (+)-thujopsene-forming)
Comments: The recombinant enzyme from the plant Arabidopsis thaliana produces 27.3% (+)-α-barbatene, 17.8% (+)-thujopsene and 9.9% (+)-β-chamigrene [1] plus traces of other sesquiterpenoids [2]. See EC 4.2.3.69 (+)-α-barbatene synthase, and EC 4.2.3.78 β-chamigrene synthase.
Links to other databases: BRENDA, EXPASY, KEGG, CAS registry number:
References:
1. Wu, S., Schoenbeck, M.A., Greenhagen, B.T., Takahashi, S., Lee, S., Coates, R.M. and Chappell, J. Surrogate splicing for functional analysis of sesquiterpene synthase genes. Plant Physiol. 138 (2005) 1322-1333. [PMID: 15965019]
2. Tholl, D., Chen, F., Petri, J., Gershenzon, J. and Pichersky, E. Two sesquiterpene synthases are responsible for the complex mixture of sesquiterpenes emitted from Arabidopsis flowers. Plant J. 42 (2005) 757-771. [PMID: 15918888]
Accepted name: α-longipinene synthase
Reaction: (2E,6E)-farnesyl diphosphate = α-longipinene + diphosphate
For diagram of reaction click here and mechanism click here.
Systematic name: (2E,6E)-farnesyl-diphosphate diphosphate-lyase (α-longipinene-forming)
Comments: The enzyme from Norway spruce produces longifolene as the main product (c.f. EC 4.2.3.58, longifolene synthase). α-Longipinene constitutes about 15% of the total products.
Links to other databases: BRENDA, EXPASY, KEGG, CAS registry number:
References:
1. Martin, D.M., Faldt, J. and Bohlmann, J. Functional characterization of nine Norway Spruce TPS genes and evolution of gymnosperm terpene synthases of the TPS-d subfamily. Plant Physiol. 135 (2004) 1908-1927. [PMID: 15310829]
2. Köpke, D., Schröder, R., Fischer, H.M., Gershenzon, J., Hilker, M. and Schmidt, A. Does egg deposition by herbivorous pine sawflies affect transcription of sesquiterpene synthases in pine? Planta 228 (2008) 427-438. [PMID: 18493792]
Accepted name: exo-α-bergamotene synthase
Reaction: (2E,6E)-farnesyl diphosphate = (–)-exo-α-bergamotene + diphosphate
For diagram of reaction click here and mechanism click here.
Glossary: (–)-exo-α-bergamotene = (–)-trans-α-bergamotene = (1S,5S,6R)-2,6-dimethyl-6-(4-methylpent-3-en-1-yl)bicyclo[3.1.1]hept-2-ene
Other name(s): trans-α-bergamotene synthase; LaBERS (gene name)
Systematic name: (2E,6E)-farnesyl diphosphate lyase (cyclizing, (–)-exo-α-bergamotene-forming)
Comments: The enzyme synthesizes a mixture of sesquiterpenoids from (2E,6E)-farnesyl diphosphate. As well as (–)-exo-α-bergamotene (74%) there were (E)-nerolidol (10%), (Z)-α-bisabolene (6%), (E)-β-farnesene (5%) and β-sesquiphellandrene (1%).
Links to other databases: BRENDA, EXPASY, KEGG, CAS registry number:
References:
1. Schnee, C., Kollner, T.G., Held, M., Turlings, T.C., Gershenzon, J. and Degenhardt, J. The products of a single maize sesquiterpene synthase form a volatile defense signal that attracts natural enemies of maize herbivores. Proc. Natl. Acad. Sci. USA 103 (2006) 1129-1134. [PMID: 16418295]
2. Landmann, C., Fink, B., Festner, M., Dregus, M., Engel, K.H. and Schwab, W. Cloning and functional characterization of three terpene synthases from lavender (Lavandula angustifolia). Arch. Biochem. Biophys. 465 (2007) 417-429. [PMID: 17662687]
Accepted name: α-santalene synthase
Reaction: (2E,6E)-farnesyl diphosphate = (+)-α-santalene + diphosphate
For diagram of reaction click here and mechanism click here.
Glossary: (–)-exo-α-bergamotene = (–)-trans-α-bergamotene = (1S,5S,6R)-2,6-dimethyl-6-(4-methylpent-3-en-1-yl)bicyclo[3.1.1]hept-2-ene
Systematic name: (2E,6E)-farnesyl diphosphate lyase (cyclizing, (+)-α-santalene-forming)
Comments: The enzyme synthesizes a mixture of sesquiterpenoids from (2E,6E)-farnesyl diphosphate. As well as (+)-α-santalene, (–)-β-santalene and (–)-exo-α-bergamotene are formed with traces of (+)-epi-β-santalene. See EC 4.2.3.83 [(–)-β-santalene synthase], and EC 4.2.3.81 [(–)-exo-α-bergamotene synthase]. cf. EC 4.2.3.50 α-santalene synthase [(2Z,6Z)-farnesyl diphosphate cyclizing]
Links to other databases: BRENDA, EXPASY, KEGG, CAS registry number:
References:
1. Jones, C.G., Moniodis, J., Zulak, K.G., Scaffidi, A., Plummer, J.A., Ghisalberti, E.L., Barbour, E.L. and Bohlmann, J. Sandalwood fragrance biosynthesis involves sesquiterpene synthases of both the terpene synthase (TPS)-a and TPS-b subfamilies, including santalene synthases. J. Biol. Chem. 286 (2011) 17445-17454. [PMID: 21454632]
Accepted name: β-santalene synthase
Reaction: (2E,6E)-farnesyl diphosphate = (–)-β-santalene + diphosphate
For diagram of reaction click here and mechanism click here.
Glossary: (–)-exo-α-bergamotene = (–)-trans-α-bergamotene = (1S,5S,6R)-2,6-dimethyl-6-(4-methylpent-3-en-1-yl)bicyclo[3.1.1]hept-2-ene
Systematic name: (2E,6E)-farnesyl diphosphate lyase (cyclizing, (–)-β-santalene-forming)
Comments: The enzyme synthesizes a mixture of sesquiterpenoids from (2E,6E)-farnesyl diphosphate. As well as (–)-β-santalene (+)-α-santalene and (–)-exo-α-bergamotene are formed with traces of (+)-epi-β-santalene. See EC 4.2.3.82 [(+)-α-santalene synthase], and EC 4.2.3.81 [(–)-exo-α-bergamotene synthase].
Links to other databases: BRENDA, EXPASY, KEGG, CAS registry number:
References:
1. Jones, C.G., Moniodis, J., Zulak, K.G., Scaffidi, A., Plummer, J.A., Ghisalberti, E.L., Barbour, E.L. and Bohlmann, J. Sandalwood fragrance biosynthesis involves sesquiterpene synthases of both the terpene synthase (TPS)-a and TPS-b subfamilies, including santalene synthases. J. Biol. Chem. 286 (2011) 17445-17454. [PMID: 21454632]
Accepted name: 10-epi-γ-eudesmol synthase
Reaction: (2E,6E)-farnesyl diphosphate + H2O = 10-epi-γ-eudesmol + diphosphate
For diagram of reaction click here and mechanism click here
Glossary: 10-epi-γ-eudesmol = 2-[(2R,4aS)-4a,8-dimethyl-1,2,3,4,4a,5,6,7-octahydronaphthalen-2-yl]propan-2-ol
Systematic name: (2E,6E)-farnesyl-diphosphate diphosphate-lyase (10-epi-γ-eudesmol-forming)
Comments: The recombinant enzyme from ginger (Zingiber zerumbet) gives 62.6% β-eudesmol, 16.8% 10-epi-γ-eudesmol, 10% α-eudesmol, and 5.6% aristolene. cf. EC 4.2.3.68 (β-eudesmol synthase) and EC 4.2.3.85 (α-eudesmol synthase)
Links to other databases: BRENDA, EXPASY, KEGG, CAS registry number:
References:
1. Yu, F., Harada, H., Yamasaki, K., Okamoto, S., Hirase, S., Tanaka, Y., Misawa, N. and Utsumi, R. Isolation and functional characterization of a β-eudesmol synthase, a new sesquiterpene synthase from Zingiber zerumbet Smith. FEBS Lett. 582 (2008) 565-572. [PMID: 18242187]
Accepted name: α-eudesmol synthase
Reaction: (2E,6E)-farnesyl diphosphate + H2O = α-eudesmol + diphosphate
For diagram of reaction click here and mechanism click here
Glossary: (–)-α-eudesmol = 2-[(2R,4aR,8aR)-4a,8-dimethyl-1,2,3,4,4a,5,6,8a-octahydronaphthalen-2-yl]propan-2-ol
Systematic name: (2E,6E)-farnesyl-diphosphate diphosphate-lyase (α-eudesmol-forming)
Comments: The recombinant enzyme from ginger (Zingiber zerumbet) gives 62.6% β-eudesmol, 16.8% 10-epi-γ-eudesmol, 10% α-eudesmol, and 5.6% aristolene. cf. EC 4.2.3.68 (β-eudesmol synthase) and EC 4.2.3.84 (10-epi-γ-eudesmol synthase)
Links to other databases: BRENDA, EXPASY, KEGG, CAS registry number:
References:
1. Yu, F., Harada, H., Yamasaki, K., Okamoto, S., Hirase, S., Tanaka, Y., Misawa, N. and Utsumi, R. Isolation and functional characterization of a β-eudesmol synthase, a new sesquiterpene synthase from Zingiber zerumbet Smith. FEBS Lett. 582 (2008) 565-572. [PMID: 18242187]
Accepted name: 7-epi-α-selinene synthase
Reaction: (2E,6E)-farnesyl diphosphate = 7-epi-α-selinene + diphosphate
For diagram of reaction click here.
Glossary: 7-epi-α-selinene = (2S,4aR,8aR)-4a,8-dimethyl-2-(prop-1-en-2-yl)-1,2,3,4,4a,5,6,8a-octahydronaphthalene
Systematic name: (2E,6E)-farnesyl-diphosphate diphosphate-lyase (7-epi-α-selinene-forming)
Comments: The recombinant enzyme from Vitis vinifera forms 49.5% (+)-valencene (cf. EC 4.2.3.73, valencene synthase) and 35.5% (–)-7-epi-α-selinene. Initial cyclization gives (+)-germacrene A in an enzyme bound form which is not released to the medium.
Links to other databases: BRENDA, EXPASY, KEGG, CAS registry number:
References:
1. Lucker, J., Bowen, P. and Bohlmann, J. Vitis vinifera terpenoid cyclases: functional identification of two sesquiterpene synthase cDNAs encoding (+)-valencene synthase and (–)-germacrene D synthase and expression of mono- and sesquiterpene synthases in grapevine flowers and berries. Phytochemistry 65 (2004) 2649-2659. [PMID: 15464152]
2. Martin, D.M., Toub, O., Chiang, A., Lo, B.C., Ohse, S., Lund, S.T. and Bohlmann, J. The bouquet of grapevine (Vitis vinifera L. cv. Cabernet Sauvignon) flowers arises from the biosynthesis of sesquiterpene volatiles in pollen grains. Proc. Natl. Acad. Sci. USA 106 (2009) 7245-7250. [PMID: 19359488]
Accepted name: α-guaiene synthase
Reaction: (2E,6E)-farnesyl diphosphate = α-guaiene + diphosphate
For diagram of reaction click here.
Other name(s): PatTps177 (gene name)
Systematic name: (2E,6E)-farnesyl-diphosphate diphosphate-lyase (cyclizing, α-guaiene-forming)
Comments: Requires Mg2+. The enzyme from Pogostemon cablin gives 13% α-guaiene as well as 37% (–)-patchoulol (see EC 4.2.3.70), 13% δ-guaiene (see EC 4.2.3.93), and traces of at least ten other sesquiterpenoids [1]. In Aquilaria crassna three clones of the enzyme gave about 80% δ-guaiene and 20% α-guaiene, with traces of α-humulene. A fourth clone gave 54% δ-guaiene and 45% α-guaiene [2].
Links to other databases: BRENDA, EXPASY, KEGG, CAS registry number:
References:
1. Deguerry, F., Pastore, L., Wu, S., Clark, A., Chappell, J. and Schalk, M. The diverse sesquiterpene profile of patchouli, Pogostemon cablin, is correlated with a limited number of sesquiterpene synthases. Arch. Biochem. Biophys. 454 (2006) 123-136. [PMID: 16970904]
2. Kumeta, Y. and Ito, M. Characterization of δ-guaiene synthases from cultured cells of Aquilaria, responsible for the formation of the sesquiterpenes in agarwood. Plant Physiol. 154 (2010) 1998-2007. [PMID: 20959422]
Accepted name: viridiflorene synthase
Reaction: (2E,6E)-farnesyl diphosphate = viridiflorene + diphosphate
For diagram of reaction click here.
Other name(s): TPS31
Systematic name: (2E,6E)-farnesyl-diphosphate diphosphate-lyase (viridiflorene-forming)
Comments: Viridiflorene is the only product of this enzyme from Solanum lycopersicum.
Links to other databases: BRENDA, EXPASY, KEGG, CAS registry number:
References:
1. Bleeker, P.M., Spyropoulou, E.A., Diergaarde, P.J., Volpin, H., De Both, M.T., Zerbe, P., Bohlmann, J., Falara, V., Matsuba, Y., Pichersky, E., Haring, M.A. and Schuurink, R.C. RNA-seq discovery, functional characterization, and comparison of sesquiterpene synthases from Solanum lycopersicum and Solanum habrochaites trichomes. Plant Mol. Biol. 77 (2011) 323-326. [PMID: 21818683]
Accepted name: (+)-β-caryophyllene synthase
Reaction: (2E,6E)-farnesyl diphosphate = (+)-β-caryophyllene + diphosphate
For diagram of reaction click here.
Other name(s): GcoA
Systematic name: (2E,6E)-farnesyl-diphosphate diphosphate-lyase [cyclizing, (+)-β-caryophyllene-forming]
Comments: A multifunctional enzyme which also converts the (+)-β-caryophyllene to (+)-caryolan-1-ol (see EC 3.7.1.15, (+)-caryolan-1-ol synthase). cf. EC 4.2.3.57 (–)-β-caryophyllene synthase.
Links to other databases: BRENDA, EXPASY, KEGG, CAS registry number:
References:
1. Nakano, C., Horinouchi, S. and Ohnishi, Y. Characterization of a novel sesquiterpene cyclase involved in (+)-caryolan-1-ol biosynthesis in Streptomyces griseus. J. Biol. Chem. 286 (2011) 27980-27987. [PMID: 21693706]
Accepted name: 5-epi-α-selinene synthase
Reaction: (2E,6E)-farnesyl diphosphate = 5-epi-α-selinene + diphosphate
For diagram of reaction click here.
Glossary: 5-epi-α-selinene = 5β-eudesma-3,11-diene = (2R,4aR,8aS)-1,2,3,4,4a,5,6,8a-octahydro-4a,8-dimethyl-2-(prop-1-en-2-yl)naphthalene;;
[= 8a-epi-α-selinene which uses naththalene numbering not eudesmane]
Other name(s): 8a-epi-α-selinene synthase; NP1
Systematic name: (2E,6E)-farnesyl-diphosphate diphosphate-lyase (cyclizing, 5-epi-α-selinene-forming)
Comments: Requires Mg2+. The enzyme forms 5-epi-α-selinene possibly via germecrene A or a 1,6-hydride shift mechanism.
Links to other databases: BRENDA, EXPASY, KEGG, CAS registry number:
References:
1. Agger, S.A., Lopez-Gallego, F., Hoye, T.R. and Schmidt-Dannert, C. Identification of sesquiterpene synthases from Nostoc punctiforme PCC 73102 and Nostoc sp. strain PCC 7120. J. Bacteriol. 190 (2008) 6084-6096. [PMID: 18658271]
Accepted name: cubebol synthase
Reaction: (2E,6E)-farnesyl diphosphate + H2O = cubebol + diphosphate
For diagram of reaction click here and mechanism click here.
Other name(s): Cop4
Systematic name: (2E,6E)-farnesyl-diphosphate diphosphate-lyase (cyclizing, cubebol-forming)
Comments: Requires Mg2+. The enzyme gives 28% cubebol, 29% (–)-germacrene D, 10% (+)-δ-cadinene and traces of several other sesquiterpenoids. See also EC 4.2.3.75 (–)-germacrene D synthase and EC 4.2.3.13 (+)-δ-cadinene synthase.
Links to other databases: BRENDA, EXPASY, KEGG, CAS registry number:
References:
1. Lopez-Gallego, F., Agger, S.A., Abate-Pella, D., Distefano, M.D. and Schmidt-Dannert, C. Sesquiterpene synthases Cop4 and Cop6 from Coprinus cinereus: catalytic promiscuity and cyclization of farnesyl pyrophosphate geometric isomers. Chembiochem. 11 (2010) 1093-1106. [PMID: 20419721]
Accepted name: (+)-γ-cadinene synthase
Reaction: (2E,6E)-farnesyl diphosphate = (+)-γ-cadinene + diphosphate
For diagram of reaction click here and mechanism click here.
Systematic name: (2E,6E)-farnesyl-diphosphate diphosphate-lyase [(+)-γ-cadinene-forming]
Comments: The cloned enzyme from the melon, Cucumis melo, gave mainly δ- and γ-cadinene with traces of several other sesquiterpenoids cf. EC 4.2.3.62 (–)-γ-cadinene synthase [(2Z,6E)-farnesyl diphosphate cyclizing]; EC 4.2.3.13 (+)-δ-cadinene synthase.
Links to other databases: BRENDA, EXPASY, KEGG, CAS registry number:
References:
1. Iijima, Y., Davidovich-Rikanati, R., Fridman, E., Gang, D.R., Bar, E., Lewinsohn, E. and Pichersky, E. The biochemical and molecular basis for the divergent patterns in the biosynthesis of terpenes and phenylpropenes in the peltate glands of three cultivars of basil. Plant Physiol. 136 (2004) 3724-3736. [PMID: 15516500]
2. Portnoy, V., Benyamini, Y., Bar, E., Harel-Beja, R., Gepstein, S., Giovannoni, J.J., Schaffer, A.A., Burger, J., Tadmor, Y., Lewinsohn, E. and Katzir, N. The molecular and biochemical basis for varietal variation in sesquiterpene content in melon (Cucumis melo L.) rinds. Plant Mol. Biol. 66 (2008) 647-661. [PMID: 18264780]
Accepted name: δ-guaiene synthase
Reaction: (2E,6E)-farnesyl diphosphate = δ-guaiene + diphosphate
For diagram of reaction click here.
Glossary: δ-guaiene = α-bulnesene
Systematic name: (2E,6E)-farnesyl-diphosphate diphosphate-lyase (cyclizing, δ-guaiene-forming)
Comments: Requires Mg2+. In Aquilaria crassna three clones of the enzyme gave about 80% δ-guaiene and 20% α-guaiene (see also EC 4.2.3.87). A fourth clone gave 54% δ-guaiene and 45% α-guaiene [2]. The enzyme from Pogostemon cablin gives 13% δ-guaiene as well as 37% (–)-patchoulol (see EC 4.2.3.70), 13% α-guaiene (see EC 4.2.3.87), and traces of at least ten other sesquiterpenoids [1].
Links to other databases: BRENDA, EXPASY, KEGG, CAS registry number:
References:
1. Deguerry, F., Pastore, L., Wu, S., Clark, A., Chappell, J. and Schalk, M. The diverse sesquiterpene profile of patchouli, Pogostemon cablin, is correlated with a limited number of sesquiterpene synthases. Arch. Biochem. Biophys. 454 (2006) 123-136. [PMID: 16970904]
2. Kumeta, Y. and Ito, M. Characterization of δ-guaiene synthases from cultured cells of Aquilaria, responsible for the formation of the sesquiterpenes in agarwood. Plant Physiol. 154 (2010) 1998-2007. [PMID: 20959422]
Accepted name: γ-curcumene synthase
Reaction: (2E,6E)-farnesyl diphosphate = γ-curcumene + diphosphate
For diagram of reaction click here and mechanism click here.
Other name(s): PatTpsA (gene name)
Systematic name: (2E,6E)-farnesyl-diphosphate diphosphate-lyase (cyclizing, γ-curcumene-forming)
Comments: One of five sesquiterpenoid synthases in Pogostemon cablin (patchouli).
Links to other databases: BRENDA, EXPASY, KEGG, CAS registry number:
References:
1. Deguerry, F., Pastore, L., Wu, S., Clark, A., Chappell, J. and Schalk, M. The diverse sesquiterpene profile of patchouli, Pogostemon cablin, is correlated with a limited number of sesquiterpene synthases. Arch. Biochem. Biophys. 454 (2006) 123-136. [PMID: 16970904]
Accepted name: (–)-α-cuprenene synthase
Reaction: (2E,6E)-farnesyl diphosphate = (–)-α-cuprenene + diphosphate
For diagram of reaction click here.
Other name(s): Cop6
Systematic name: (–)-α-cuprenene hydrolase [cyclizing, (–)-α-cuprenene-forming]
Comments: The enzyme from the fungus Coprinopsis cinerea produces (–)-α-cuprenene with high selectivity.
Links to other databases: BRENDA, EXPASY, KEGG, CAS registry number:
References:
1. Lopez-Gallego, F., Agger, S.A., Abate-Pella, D., Distefano, M.D. and Schmidt-Dannert, C. Sesquiterpene synthases Cop4 and Cop6 from Coprinus cinereus: catalytic promiscuity and cyclization of farnesyl pyrophosphate geometric isomers. Chembiochem. 11 (2010) 1093-1106. [PMID: 20419721]
Accepted name: avermitilol synthase
Reaction: (2E,6E)-farnesyl diphosphate + H2O = avermitilol + diphosphate
For diagram of reaction click here.
Systematic name: avermitilol hydrolase (cyclizing, avermitilol-forming)
Comments: Requires Mg2+. The recombinent enzyme gives avermitilol (85%) plus traces of germacrene A, germacrene B and viridiflorol. The (1S)-hydrogen of farnesyl diphosphate is retained.
Links to other databases: BRENDA, EXPASY, KEGG, CAS registry number:
References:
1. Chou, W.K., Fanizza, I., Uchiyama, T., Komatsu, M., Ikeda, H. and Cane, D.E. Genome mining in Streptomyces avermitilis: cloning and characterization of SAV_76, the synthase for a new sesquiterpene, avermitilol. J. Am. Chem. Soc. 132 (2010) 8850-8851. [PMID: 20536237]
Accepted name: (–)-δ-cadinene synthase
Reaction: (2E,6E)-farnesyl diphosphate = (–)-δ-cadinene + diphosphate
For diagram of reaction click here.
Glossary: (–)-δ-cadinene = (1R,8aS)-4,7-dimethyl-1-(propan-2-yl)-1,2,3,5,6,8a-hexahydronaphthalene
Systematic name: (2E,6E)-farnesyl diphosphate diphosphate-lyase (cyclizing, (–)-δ-cadinene-forming)
Comments: The cyclization mechanism involves an intermediate nerolidyl diphosphate leading to a helminthogermacradienyl cation. Following a 1,3-hydride shift of the original 1-pro-S hydrogen of (2E,6E)-farnesyl diphosphate, cyclization and deprotonation gives (–)-δ-cadinene.
Links to other databases: BRENDA, EXPASY, KEGG, CAS registry number:
References:
1. Hu, Y., Chou, W.K., Hopson, R. and Cane, D.E. Genome mining in Streptomyces clavuligerus: expression and biochemical characterization of two new cryptic sesquiterpene synthases. Chem. Biol. 18 (2011) 32-37. [PMID: 21276937]
Accepted name: (+)-T-muurolol synthase
Reaction: (2E,6E)-farnesyl diphosphate + H2O = (+)-T-muurolol + diphosphate
For diagram of reaction click here.
Glossary: (+)-T-muurolol = (1R,4R,4aS,8aR)-1,6-dimethyl-4-(propan-2-yl)-1,2,3,4,4a,7,8,8a-octahydronaphthalen-1-ol
Systematic name: (2E,6E)-farnesyl-diphosphate diphosphate-lyase (cyclizing, (+)-T-muurolol-forming)
Comments: The cyclization mechanism involves an intermediate nerolidyl diphosphate leading to a helminthogermacradienyl cation. After a 1,3-hydride shift of the original 1-pro-S hydrogen of farnesyl diphosphate, cyclization and deprotonation result in (+)-T-muurolol.
Links to other databases: BRENDA, EXPASY, KEGG, CAS registry number:
References:
1. Hu, Y., Chou, W.K., Hopson, R. and Cane, D.E. Genome mining in Streptomyces clavuligerus: expression and biochemical characterization of two new cryptic sesquiterpene synthases. Chem. Biol. 18 (2011) 32-37. [PMID: 21276937]
Accepted name: labdatriene synthase
Reaction: 9α-copalyl diphosphate = (12E)-9α-labda-8(17),12,14-triene + diphosphate
For diagram of reaction click here.
Glossary: 9α-copalyl diphosphate = syn-copalyl diphosphate = (2E)-3-methyl-5-[(1R,4aS,8aS)-5,5,8a-trimethyl-2-methylidenedecahydronaphthalen-1-yl]pent-2-en-1-yl trihydrogen diphosphate
(12E)-9α-labda-8(17),12,14-triene = (4aS,5R,8aS)-1,1,4a-trimethyl-6-methylidene-5-[(2E)-3-methylpenta-2,4-dien-1-yl]decahydronaphthalene
Other name(s): OsKSL10 (gene name)
Systematic name: 9α-copalyl-diphosphate diphosphate-lyase [(12E)-9α-labda-8(17),12,14-triene-forming]
Comments: The enzyme from rice (Oryza sativa), expressed in Escherichia coli, also produces ent-sandaracopimara-8(14),15-diene from ent-copalyl diphosphate, another naturally occuring copalyl isomer in rice (cf. ent-sandaracopimaradiene synthase, EC 4.2.3.29).
Links to other databases: BRENDA, EXPASY, KEGG, CAS registry number:
References:
1. Morrone, D., Hillwig, M.L., Mead, M.E., Lowry, L., Fulton, D.B. and Peters, R.J. Evident and latent plasticity across the rice diterpene synthase family with potential implications for the evolution of diterpenoid metabolism in the cereals. Biochem. J. 435 (2011) 589-595. [PMID: 21323642]
Accepted name: bicyclogermacrene synthase
Reaction: (2E,6E)-farnesyl diphosphate = bicyclogermacrene + diphosphate
For diagram of reaction click here.
Other name(s): Ov-TPS4
Systematic name: (2E,6E)-farnesyl-diphosphate diphosphate-lyase (bicyclogermacrene-forming)
Comments: The enzyme from oregano (Origanum vulgare) gives mainly bicyclogermacrene with Mn2+ as a cofactor. With Mg2+ a more complex mixture is produced.
Links to other databases: BRENDA, EXPASY, KEGG, CAS registry number:
References:
1. Crocoll, C., Asbach, J., Novak, J., Gershenzon, J. and Degenhardt, J. Terpene synthases of oregano (Origanum vulgare L.) and their roles in the pathway and regulation of terpene biosynthesis. Plant Mol. Biol. 73 (2010) 587-603. [PMID: 20419468]
Accepted name: 7-epi-sesquithujene synthase
Reaction: (2E,6E)-farnesyl diphosphate = 7-epi-sesquithujene + diphosphate
For diagram of reaction click here and mechanism click here.
Other name(s): TPS4-B73
Systematic name: (2E,6E)-farnesyl-diphosphate diphosphate-lyase (7-epi-sesquithujene-forming)
Comments: The enzyme from Zea mays, variety B73, gives mainly 7-epi-sesquithujene with (S)-β-bisabolene and traces of other sesquiterpenoids, cf. EC 4.2.3.55 (S)-β-bisabolene synthase. It requires Mg2+ or Mn2+. The product ratio is dependent on which metal ion is present. 7-epi-Sesquithujene is an attractant for the emerald ash borer beetle.
Links to other databases: BRENDA, EXPASY, KEGG, CAS registry number:
References:
1. Köllner, T.G., Schnee, C., Gershenzon, J. and Degenhardt, J. The variability of sesquiterpenes emitted from two Zea mays cultivars is controlled by allelic variation of two terpene synthase genes encoding stereoselective multiple product enzymes. Plant Cell 16 (2004) 1115-1131. [PMID: 15075399]
Accepted name: sesquithujene synthase
Reaction: (2E,6E)-farnesyl diphosphate = sesquithujene + diphosphate
For diagram of reaction click here and mechanism click here.
Other name(s): TPS5-Del1
Systematic name: (2E,6E)-farnesyl-diphosphate diphosphate-lyase (sesquithujene-forming)
Comments: The enzyme from Zea mays, variety Delprim, gives mainly sesquithujene with (S)-β-bisabolene and (E)-β-farnesene plus traces of other sesquiterpenoids, cf. EC 4.2.3.55 [(S)-β-bisabolene synthase] and EC 4.2.3.47 (β-farnesene synthase). It requires Mg2+ or Mn2+. The exact product ratio is dependent on which metal ion is present.
Links to other databases: BRENDA, EXPASY, KEGG, CAS registry number:
References:
1. Köllner, T.G., Schnee, C., Gershenzon, J. and Degenhardt, J. The variability of sesquiterpenes emitted from two Zea mays cultivars is controlled by allelic variation of two terpene synthase genes encoding stereoselective multiple product enzymes. Plant Cell 16 (2004) 1115-1131. [PMID: 15075399]
Accepted name: ent-isokaurene synthase
Reaction: ent-copalyl diphosphate = ent-isokaurene + diphosphate
For diagram of reaction click here and mechanism click here.
Other name(s): OsKSL5i; OsKSL6
Systematic name: ent-copalyl-diphosphate diphosphate-lyase (cyclizing, ent-isokaurene-forming)
Comments: Two enzymes of the rice sub-species Oryza sativa ssp. indica, OsKSL5 and OsKSL6, produce ent-isokaurene. A variant of OsKSL5 from the sub-species Oryza sativa ssp. japonica produces ent-pimara-8(14),15-diene instead [cf. EC 4.2.3.30, ent-pimara-8(14),15-diene synthase].
Links to other databases: BRENDA, EXPASY, KEGG, CAS registry number:
References:
1. Xu, M., Wilderman, P.R., Morrone, D., Xu, J., Roy, A., Margis-Pinheiro, M., Upadhyaya, N.M., Coates, R.M. and Peters, R.J. Functional characterization of the rice kaurene synthase-like gene family. Phytochemistry 68 (2007) 312-326. [PMID: 17141283]
2. Xu, M., Wilderman, P.R. and Peters, R.J. Following evolution’s lead to a single residue switch for diterpene synthase product outcome. Proc. Natl. Acad. Sci. USA 104 (2007) 7397-7401. [PMID: 17456599]
Accepted name: α-humulene synthase
Reaction: (2E,6E)-farnesyl diphosphate = α-humulene + diphosphate
For diagram of reaction click here.
Other name(s): ZSS1
Systematic name: (2E,6E)-farnesyl-diphosphate diphosphate-lyase (α-humulene-forming)
Comments: The enzyme from Zingiber zerumbet, shampoo ginger, also gives traces of β-caryophyllene.
Links to other databases: BRENDA, EXPASY, KEGG, CAS registry number:
References:
1. Yu, F., Okamto, S., Nakasone, K., Adachi, K., Matsuda, S., Harada, H., Misawa, N. and Utsumi, R. Molecular cloning and functional characterization of α-humulene synthase, a possible key enzyme of zerumbone biosynthesis in shampoo ginger (Zingiber zerumbet Smith). Planta 227 (2008) 1291-1299. [PMID: 18273640]
[EC 4.2.99.2 Transferred entry: now EC 4.2.3.1, threonine synthase (EC 4.2.99.2 created 1961, deleted 2000)]
[EC 4.2.99.3 Transferred entry: now EC 4.2.2.2 pectate lyase (EC 4.2.99.3 created 1965, deleted 1972)]
[EC 4.2.99.4 Transferred entry: now EC 4.2.2.3 alginate lyase (EC 4.2.99.4 created 1965, deleted 1972)]
[EC 4.2.99.5 Deleted entry: polyglucuronide lyase (EC 4.2.99.5 created 1965, deleted 1972)]
[EC 4.2.99.6 Deleted entry: chondroitin sulfate lyase. Now included with EC 4.2.2.4 (chondroitin ABC lyase) and EC 4.2.2.5 (chondroitin AC lyase) (EC 4.2.99.6 created 1965, deleted 1972)]
[EC 4.2.99.7 Transferred entry: now EC 4.2.3.2, ethanolamine-phosphate phospho-lyase (EC 4.2.99.7 created 1972, deleted 2000)]
[EC 4.2.99.8 Transferred entry: now EC 2.5.1.47, cysteine synthase (EC 4.2.99.8 created 1972, modified 1976, modified 1990, deleted 2002)]
[EC 4.2.99.9 Transferred entry: now EC 2.5.1.48, cystathionine γ-synthase (EC 4.2.99.9 created 1972, deleted 2002)]
[EC 4.2.99.10 Transferred entry: now EC 2.5.1.49, O-acetylhomoserine aminocarboxypropyltransferase (EC 4.2.99.10 created 1972, deleted 2002)]
[EC 4.2.99.11 Transferred entry: now EC 4.2.3.3, methylglyoxal synthase (EC 4.2.99.11 created 1972, deleted 2000)]
Accepted name: carboxymethyloxysuccinate lyase
Reaction: carboxymethyloxysuccinate = fumarate + glycolate
Other name(s): carbon-oxygen lyase; carboxymethyloxysuccinate glycolate-lyase
Systematic name: carboxymethyloxysuccinate glycolate-lyase (fumarate-forming)
Links to other databases: BRENDA, EXPASY, KEGG, CAS registry number: 53167-89-8
References:
1. Peterson, D. and Llaneza, J. Identification of a carbon-oxygen lyase activity cleaving the ether linkage in carboxymethyloxysuccinic acid. Arch. Biochem. Biophys. 162 (1974) 135-146. [PMID: 4831330]
[EC 4.2.99.13 Transferred entry: now EC 2.5.1.50, zeatin 9-aminocarboxyethyltransferase (EC 4.2.99.13 created 1984, deleted 2002)]
[EC 4.2.99.14 Transferred entry: now EC 2.5.1.51, β-pyrazolylalanine synthase (EC 4.2.99.14 created 1989 (EC 4.2.99.17 incorporated 1992), deleted 2002)]
[EC 4.2.99.15 Transferred entry: now EC 2.5.1.52, L-mimosine synthase (EC 4.2.99.15 created 1989, deleted 2002)]
[EC 4.2.99.16 Transferred entry: now EC 2.5.1.53, uracilylalanine synthase (EC 4.2.99.16 created 1990, deleted 2002)]
[EC 4.2.99.17 Deleted entry: listed as EC 4.2.99.14 β-pyrazolylalanine synthase (acetylserine) (EC 4.2.99.17 created 1992, deleted 1992)]
Accepted name: DNA-(apurinic or apyrimidinic site) lyase
Reaction: The C-O-P bond 3' to the apurinic or apyrimidinic site in DNA is broken by a β-elimination reaction, leaving a 3'-terminal unsaturated sugar and a product with a terminal 5'-phosphate
Other name(s): AP lyase; AP endonuclease class I; endodeoxyribonuclease (apurinic or apyrimidinic); deoxyribonuclease (apurinic or apyrimidinic); E. coli endonuclease III; phage-T4 UV endonuclease; Micrococcus luteus UV endonuclease; AP site-DNA 5'-phosphomonoester-lyase; X-ray endonuclease III
Systematic name: DNA-(apurinic or apyrimidinic site) 5'-phosphomonoester-lyase
Comments: 'Nicking' of the phosphodiester bond is due to a lyase-type reaction, not hydrolysis. This group of enzymes was previously listed as endonucleases, under EC 3.1.25.2.
Links to other databases: BRENDA, EXPASY, KEGG, PDB, CAS registry number: 61811-29-8
References:
1. Bailly, V., Sente, B. and Verly, W.G. Bacteriophage-T4 and Micrococcus luteus UV endonucleases are not endonucleases but β-elimination and sometimes βδ-elimination catalysts. Biochem. J. 259 (1989) 751-759. [PMID: 2471512]
2. Bailly, V. and Verly, W.G. Escherichia coli endonuclease III is not an endonuclease but a β-elimination catalyst. Biochem. J. 242 (1987) 565-572. [PMID: 2439070]
3. Bailly, V. and Verly, W.G. AP endonucleases and AP lyases. Nucleic Acids Res. 17 (1989) 3617-3618. [PMID: 2471157]
4. Manoharan, M., Mazumder, A., Ransom, S.C., Gerlt, J.A. and Bolton, P.H. Mechanism of UV endonuclease-V cleavage of abasic sites in DNA determined by C-13 labeling. J. Am. Chem. Soc. 110 (1988) 2690-2691.
[EC 4.2.99.19 Transferred entry: Now EC 4.4.1.23, 2-hydroxypropyl-CoM lyase. The enzyme was incorrectly classified as acting on a C-O bond rather than a C-S bond (EC 4.2.99.19 created 2001, deleted 2005)]
Accepted name: 2-succinyl-6-hydroxy-2,4-cyclohexadiene-1-carboxylate synthase
Reaction: 5-enolpyruvoyl-6-hydroxy-2-succinylcyclohex-3-ene-1-carboxylate = (1R,6R)-6-hydroxy-2-succinylcyclohexa-2,4-diene-1-carboxylate + pyruvate
For diagram of reaction, click here.
Other name(s): 2-succinyl-6-hydroxy-2,4-cyclohexadiene-1-carboxylic acid synthase; 6-hydroxy-2-succinylcyclohexa-2,4-diene-1-carboxylate synthase; SHCHC synthase; MenH; YfbB
Systematic name: 5-enolpyruvoyl-6-hydroxy-2-succinylcyclohex-3-ene-1-carboxylate pyruvate-lyase [(1R,6R)-6-hydroxy-2-succinylcyclohexa-2,4-diene-1-carboxylate-forming)
Comments: This enzyme is involved in the biosynthesis of vitamin K2 (menaquinone). In most anaerobes and all Gram-positive aerobes, menaquinone is the sole electron transporter in the respiratory chain and is essential for their survival. It had previously been thought that the reactions carried out by this enzyme and EC 2.2.1.9, 2-succinyl-5-enolpyruvyl-6-hydroxy-3-cyclohexene-1-carboxylic-acid synthase, were carried out by a single enzyme but this has since been disproved [2].
Links to other databases: BRENDA, EXPASY, KEGG, CAS registry number: 122007-88-9
References:
1. Jiang, M., Chen, X., Guo, Z.F., Cao, Y., Chen, M. and Guo, Z. Identification and characterization of (1R,6R)-2-succinyl-6-hydroxy-2,4-cyclohexadiene-1-carboxylate synthase in the menaquinone biosynthesis of Escherichia coli. Biochemistry 47 (2008) 3426-3434. [PMID: 18284213]
2. Jiang, M., Cao, Y., Guo, Z.F., Chen, M., Chen, X. and Guo, Z. Menaquinone biosynthesis in Escherichia coli: identification of 2-succinyl-5-enolpyruvyl-6-hydroxy-3-cyclohexene-1-carboxylate as a novel intermediate and re-evaluation of MenD activity. Biochemistry 46 (2007) 10979-10989. [PMID: 17760421]
Accepted name: isochorismate lyase
Reaction: isochorismate = salicylate + pyruvate
Other name(s): salicylate biosynthesis protein pchB; pyochelin biosynthetic protein PchB; isochorismate pyruvate lyase
Systematic name: isochorismate pyruvate-lyase (salicylate-forming)
Comments: This enzyme is part of the pathway of salicylate formation from chorismate, and forms an integral part of pathways that produce salicylate-derived siderophores, such as pyochelin and yersiniabactin.
Links to other databases: BRENDA, EXPASY, KEGG, CAS registry number:
References:
1. Serino, L., Reimmann, C., Baur, H., Beyeler, M., Visca, P. and Haas, D. Structural genes for salicylate biosynthesis from chorismate in Pseudomonas aeruginosa. Mol. Gen. Genet. 249 (1995) 217-228. [PMID: 7500944]
2. Kerbarh, O., Ciulli, A., Howard, N.I. and Abell, C. Salicylate biosynthesis: overexpression, purification, and characterization of Irp9, a bifunctional salicylate synthase from Yersinia enterocolitica. J. Bacteriol. 187 (2005) 5061-5066. [PMID: 16030197]