Enzyme Nomenclature

EC 4.2.3 (continued)

Acting on Phosphates

Continued from EC 4.2.3.1 to EC 4.2.3.50, EC 4.2.3.101 to EC 4.2.3.150, and. EC 4.2.3.151 to EC 4.2.3.205

Contents

EC 4.2.3.51 β-phellandrene synthase (neryl-diphosphate-cyclizing)
EC 4.2.3.52 (4S)-β-phellandrene synthase (geranyl-diphosphate-cyclizing)
EC 4.2.3.53 (+)-endo-β-bergamotene synthase [(2Z,6Z)-farnesyl diphosphate cyclizing]
EC 4.2.3.54 (–)-endo-α-bergamotene synthase [(2Z,6Z)-farnesyl diphosphate cyclizing]
EC 4.2.3.55 (S)-β-bisabolene synthase
EC 4.2.3.56 γ-humulene synthase
EC 4.2.3.57 (–)-β-caryophyllene synthase
EC 4.2.3.58 longifolene synthase
EC 4.2.3.59 (E)-γ-bisabolene synthase
EC 4.2.3.60 germacrene C synthase
EC 4.2.3.61 5-epiaristolochene synthase
EC 4.2.3.62 (–)-γ-cadinene synthase [(2Z,6E)-farnesyl diphosphate cyclizing]
EC 4.2.3.63 (+)-cubenene synthase
EC 4.2.3.64 (+)-epicubenol synthase
EC 4.2.3.65 zingiberene synthase
EC 4.2.3.66 β-selinene cyclase
EC 4.2.3.67 cis-muuroladiene synthase
EC 4.2.3.68 β-eudesmol synthase
EC 4.2.3.69 (+)-α-barbatene synthase
EC 4.2.3.70 patchoulol synthase
EC 4.2.3.71 (E,E)-germacrene B synthase
EC 4.2.3.72 α-gurjunene synthase
EC 4.2.3.73 valencene synthase
EC 4.2.3.74 presilphiperfolanol synthase
EC 4.2.3.75 (–)-germacrene D synthase
EC 4.2.3.76 (+)-δ-selinene synthase
EC 4.2.3.77 (+)-germacrene D synthase
EC 4.2.3.78 β-chamigrene synthase
EC 4.2.3.79 thujopsene synthase
EC 4.2.3.80 α-longipinene synthase
EC 4.2.3.81 exo-α-bergamotene synthase
EC 4.2.3.82 α-santalene synthase
EC 4.2.3.83 β-santalene synthase
EC 4.2.3.84 10-epi-γ-eudesmol synthase
EC 4.2.3.85 α-eudesmol synthase
EC 4.2.3.86 7-epi-α-selinene synthase
EC 4.2.3.87 α-guaiene synthase
EC 4.2.3.88 viridiflorene synthase
EC 4.2.3.89 (+)-β-caryophyllene synthase
EC 4.2.3.90 5-epi-α-selinene synthase
EC 4.2.3.91 cubebol synthase
EC 4.2.3.92 (+)-γ-cadinene synthase
EC 4.2.3.93 δ-guaiene synthase
EC 4.2.3.94 γ-curcumene synthase
EC 4.2.3.95 (–)-α-cuprenene synthase
EC 4.2.3.96 avermitilol synthase
EC 4.2.3.97 (–)-δ-cadinene synthase
EC 4.2.3.98 (+)-T-muurolol synthase
EC 4.2.3.99 labdatriene synthase
EC 4.2.3.100 bicyclogermacrene synthase
See the following files for:
EC 4.2.3.1 to EC 4.2.3.50, EC 4.2.3.101 to EC 4.2.3.150 and EC 4.2.3.151 to EC 4.2.3.205.


Entries

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, 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]

[EC 4.2.3.51 created 2010]

EC 4.2.3.52

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, Metacyc, 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]

[EC 4.2.3.52 created 2010]

EC 4.2.3.53

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, Metacyc, 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]

[EC 4.2.3.53 created 2010]

EC 4.2.3.54

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, Metacyc, 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]

[EC 4.2.3.54 created 2010]

EC 4.2.3.55

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, Metacyc, 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]

[EC 4.2.3.55 created 2011]

EC 4.2.3.56

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, Metacyc, 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]

[EC 4.2.3.56 created 2011]

EC 4.2.3.57

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, Metacyc, 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]

[EC 4.2.3.57 created 2011, modified 2011]

EC 4.2.3.58

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, Metacyc, 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]

[EC 4.2.3.58 created 2011]

EC 4.2.3.59

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]

Links to other databases: BRENDA, EXPASY, KEGG, Metacyc, CAS registry number:

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]

[EC 4.2.3.59 created 2011]

EC 4.2.3.60

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, Metacyc, 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]

[EC 4.2.3.60 created 2011]

EC 4.2.3.61

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, Metacyc, PDB, 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]

[EC 4.2.3.61 created 2011]

EC 4.2.3.62

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, Metacyc, 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.

[EC 4.2.3.62 created 2011, modified 2011]

EC 4.2.3.63

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, Metacyc, 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.

[EC 4.2.3.63 created 2011]

EC 4.2.3.64

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, Metacyc, 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.

[EC 4.2.3.64 created 2011]

EC 4.2.3.65

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, Metacyc, 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]

[EC 4.2.3.65 created 2011]

EC 4.2.3.66

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, Metacyc, 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.

[EC 4.2.3.66 created 2011]

EC 4.2.3.67

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, Metacyc, 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]

[EC 4.2.3.67 created 2011]

EC 4.2.3.68

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, Metacyc, 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]

[EC 4.2.3.68 created 2011, modified 2011, modified 2012]

EC 4.2.3.69

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, Metacyc, 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]

[EC 4.2.3.69 created 2011, modified 2012]

EC 4.2.3.70

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, Metacyc, 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]

[EC 4.2.3.70 created 2011]

EC 4.2.3.71

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, Metacyc, 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]

[EC 4.2.3.71 created 2011]

EC 4.2.3.72

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, Metacyc, 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]

[EC 4.2.3.72 created 2011]

EC 4.2.3.73

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, Metacyc, 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]

[EC 4.2.3.73 created 2011]

EC 4.2.3.74

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, Metacyc, 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]

[EC 4.2.3.74 created 2011]

EC 4.2.3.75

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, Metacyc, 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]

[EC 4.2.3.75 created 2011]

EC 4.2.3.76

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, Metacyc, 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]

[EC 4.2.3.76 created 2011]

EC 4.2.3.77

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, Metacyc, 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]

[EC 4.2.3.77 created 2011]

EC 4.2.3.78

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, Metacyc, 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]

[EC 4.2.3.78 created 2011]

EC 4.2.3.79

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, Metacyc, 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]

[EC 4.2.3.79 created 2011]

EC 4.2.3.80

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, Metacyc, 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]

[EC 4.2.3.80 created 2011]

EC 4.2.3.81

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, Metacyc, 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]

[EC 4.2.3.81 created 2011]

EC 4.2.3.82

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, Metacyc, 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]

[EC 4.2.3.82 created 2011]

EC 4.2.3.83

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, Metacyc, 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]

[EC 4.2.3.83 created 2011]

EC 4.2.3.84

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, Metacyc, 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]

[EC 4.2.3.84 created 2011]

EC 4.2.3.85

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, Metacyc, 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]

[EC 4.2.3.85 created 2011]

EC 4.2.3.86

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, Metacyc, 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]

[EC 4.2.3.86 created 2011]

EC 4.2.3.87

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, Metacyc, 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]

[EC 4.2.3.87 created 2011]

EC 4.2.3.88

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, Metacyc, 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]

[EC 4.2.3.88 created 2011]

EC 4.2.3.89

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 4.2.1.138, (+)-caryolan-1-ol synthase). cf. EC 4.2.3.57 (–)-β-caryophyllene synthase.

Links to other databases: BRENDA, EXPASY, KEGG, Metacyc, 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]

[EC 4.2.3.89 created 2011]

EC 4.2.3.90

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, Metacyc, 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]

[EC 4.2.3.90 created 2011]

EC 4.2.3.91

Accepted name: cubebol synthase

Reaction: (2E,6E)-farnesyl diphosphate + H2O = cubebol + diphosphate

For diagram of reaction 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, Metacyc, 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]

[EC 4.2.3.91 created 2011]

EC 4.2.3.92

Accepted name: (+)-γ-cadinene synthase

Reaction: (2E,6E)-farnesyl diphosphate = (+)-γ-cadinene + diphosphate

For diagram of reaction 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, Metacyc, 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]

[EC 4.2.3.92 created 2011]

EC 4.2.3.93

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, Metacyc, 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]

[EC 4.2.3.93 created 2011]

EC 4.2.3.94

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, Metacyc, 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]

[EC 4.2.3.94 created 2012]

EC 4.2.3.95

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, Metacyc, 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]

[EC 4.2.3.95 created 2012]

EC 4.2.3.96

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, Metacyc, 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]

[EC 4.2.3.96 created 2012]

EC 4.2.3.97

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, Metacyc, 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]

[EC 4.2.3.97 created 2012]

EC 4.2.3.98

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, Metacyc, 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]

[EC 4.2.3.98 created 2012]

EC 4.2.3.99

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, Metacyc, 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]

[EC 4.2.3.99 created 2012]

EC 4.2.3.100

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, Metacyc, 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]

[EC 4.2.3.100 created 2012]


Continued with EC 4.2.3.101-156
Return to EC 4 home page
Return to Enzymes home page
Return to IUBMB Biochemical Nomenclature home page