EC 4.2.3.1 to EC 4.2.3.50, EC 4.2.3.51 to EC 4.2.3.100 and EC 4.2.3.101 to EC 4.2.3.150 .
Accepted name: pentamethylcyclopentadecatrienol synthase
Reaction: geranylgeranyl diphosphate + H2O = (1S,4E,8E,12E)-2,2,5,9,13-pentamethylcyclopentadeca-4,8,12-trien-1-ol + diphosphate
For diagram of reaction click here.
Other name(s): DtcycB (gene name)
Systematic name: geranylgeranyl-diphosphate diphosphate-lyase [(1S,4E,8E,12E)-2,2,5,9,13-pentamethylcyclopentadeca-4,8,12-trien-1-ol-forming]
Comments: Requires Mg2+. Isolated from the bacterium Streptomyces sp. SANK 60404. This trifunctional enzyme, which contains a [4Fe-4S] cluster, also produces (R)-nephthenol and (R)-cembrene A. See EC 4.2.3.150, cembrene A synthase and EC 4.2.3.149, nephthenol synthase.
Links to other databases: BRENDA, EXPASY, KEGG, MetaCyc, CAS registry number:
References:
1. Meguro, A., Tomita, T., Nishiyama, M. and Kuzuyama, T. Identification and characterization of bacterial diterpene cyclases that synthesize the cembrane skeleton. Chembiochem 14 (2013) 316-321. [PMID: 23386483]
Accepted name: 2-epi-5-epi-valiolone synthase
Reaction: α-D-sedoheptulopyranose 7-phosphate = 2-epi-5-epi-valiolone + phosphate
For diagram of reaction click here.
Glossary: 2-epi-5-epi-valiolone = (2S,3S,4S,5R)-2,3,4,5-tetrahydroxy-5-(hydroxymethyl)cyclohexan-1-one
Other name(s): AcbC; ValA; CetA; SalQ; C7-cyclitol synthase
Systematic name: α-D-sedoheptulopyranose-7-phosphate phosphate-lyase (cyclizing; 2-epi-5-epi-valiolone-forming)
Comments: The enzyme is highly specific for α-D-sedoheptulopyranose 7-phosphate. It requires a divalent metal ion (Zn2+ or Co2+) and an NAD+ cofactor, which is transiently reduced during the reaction.The enzyme is involved in the biosynthesis of C7N-aminocyclitol natural products, such as the valienamine moiety of the antidiabetic drug acarbose and the crop protectant validamycin A. cf. EC 4.2.3.155, 2-epi-valiolone synthase and EC 4.2.3.154, desmethyl-4-deoxygadusol synthase.
Links to other databases: BRENDA, EXPASY, KEGG, MetaCyc, PDB, CAS registry number:
References:
1. Stratmann, A., Mahmud, T., Lee, S., Distler, J., Floss, H.G. and Piepersberg, W. The AcbC protein from Actinoplanes species is a C7-cyclitol synthase related to 3-dehydroquinate synthases and is involved in the biosynthesis of the α-glucosidase inhibitor acarbose. J. Biol. Chem. 274 (1999) 10889-10896. [PMID: 10196166]
2. Yu, Y., Bai, L., Minagawa, K., Jian, X., Li, L., Li, J., Chen, S., Cao, E., Mahmud, T., Floss, H.G., Zhou, X. and Deng, Z. Gene cluster responsible for validamycin biosynthesis in Streptomyces hygroscopicus subsp. jinggangensis 5008. Appl. Environ. Microbiol. 71 (2005) 5066-5076. [PMID: 16151088]
3. Wu, X., Flatt, P.M., Schlorke, O., Zeeck, A., Dairi, T. and Mahmud, T. A comparative analysis of the sugar phosphate cyclase superfamily involved in primary and secondary metabolism. Chembiochem 8 (2007) 239-248. [PMID: 17195255]
4. Choi, W.S., Wu, X., Choeng, Y.H., Mahmud, T., Jeong, B.C., Lee, S.H., Chang, Y.K., Kim, C.J. and Hong, S.K. Genetic organization of the putative salbostatin biosynthetic gene cluster including the 2-epi-5-epi-valiolone synthase gene in Streptomyces albus ATCC 21838. Appl. Microbiol. Biotechnol. 80 (2008) 637-645. [PMID: 18648803]
5. Kean, K.M., Codding, S.J., Asamizu, S., Mahmud, T. and Karplus, P.A. Structure of a sedoheptulose 7-phosphate cyclase: ValA from Streptomyces hygroscopicus. Biochemistry 53 (2014) 4250-4260. [PMID: 24832673]
Accepted name: (5-formylfuran-3-yl)methyl phosphate synthase
Reaction: (5-formylfuran-3-yl)methyl phosphate + phosphate + 2 H2O = 2 D-glyceraldehyde 3-phosphate
For diagram of reaction click here.
Glossary: (5-formylfuran-3-yl)methyl phosphate = 4-(hydroxymethyl)furan-2-carboxaldehyde phosphate
Other name(s): mfnB (gene name); 4-HFC-P synthase; 4-(hydroxymethyl)-2-furaldehyde phosphate synthase
Systematic name: D-glyceraldehyde-3-phosphate phosphate-lyase [D-glyceraldehyde-3-phosphate-adding; (5-formylfuran-3-yl)methyl-phosphate-forming]
Comments: The enzyme catalyses the reaction in the direction of producing (5-formylfuran-3-yl)methyl phosphate, an intermediate in the biosynthesis of methanofuran. The sequence of events starts with the removal of a phosphate group, followed by aldol condensation and cyclization. Methanofuran is a carbon-carrier cofactor involved in the first step of the methanogenic reduction of carbon dioxide by methanogenic archaea.
Links to other databases: BRENDA, EXPASY, KEGG, MetaCyc, PDB, CAS registry number:
References:
1. Miller, D., Wang, Y., Xu, H., Harich, K. and White, R.H. Biosynthesis of the 5-(aminomethyl)-3-furanmethanol moiety of methanofuran. Biochemistry 53 (2014) 4635-4647. [PMID: 24977328]
2. Bobik, T.A., Morales, E.J., Shin, A., Cascio, D., Sawaya, M.R., Arbing, M., Yeates, T.O. and Rasche, M.E. Structure of the methanofuran/methanopterin-biosynthetic enzyme MJ1099 from Methanocaldococcus jannaschii. Acta Crystallogr. F Struct. Biol. Commun. 70 (2014) 1472-1479. [PMID: 25372812]
3. Wang, Y., Jones, M.K., Xu, H., Ray, W.K. and White, R.H. Mechanism of the enzymatic synthesis of 4-(hydroxymethyl)-2-furancarboxaldehyde-phosphate (4-HFC-P) from glyceraldehyde-3-phosphate catalyzed by 4-HFC-P synthase. Biochemistry 54 (2015) 2997-3008. [PMID: 25905665]
Accepted name: demethyl-4-deoxygadusol synthase
Reaction: D-sedoheptulose 7-phosphate = demethyl-4-deoxygadusol + phosphate + H2O
For diagram of reaction click here.
Glossary: demethyl-4-deoxygadusol = 2,3,5-trihydroxy-5-(hydroxymethyl)cyclohex-2-en-1-one
Other name(s): Nos2 (gene name); Anb2 (gene name)
Systematic name: D-sedoheptulose-7-phosphate phosphate-lyase (cyclizing; demethyl-4-deoxygadusol-forming)
Comments: The enzyme, characterized from the cyanobacterium Nostoc punctiforme PCC 73102, is involved in the biosynthesis of the sunscreen compound shinorine. It requires a divalent metal ion (Zn2+ or Co2+) and an NAD+ cofactor, which is transiently reduced during the reaction. cf. EC 4.2.3.152, 2-epi-5-epi-valiolone synthase and EC 4.2.3.155, 2-epi-valiolone synthase.
Links to other databases: BRENDA, EXPASY, KEGG, MetaCyc, PDB, CAS registry number:
References:
1. Balskus, E.P. and Walsh, C.T. The genetic and molecular basis for sunscreen biosynthesis in cyanobacteria. Science 329 (2010) 1653-1656. [PMID: 20813918]
2. Asamizu, S., Xie, P., Brumsted, C.J., Flatt, P.M. and Mahmud, T. Evolutionary divergence of sedoheptulose 7-phosphate cyclases leads to several distinct cyclic products. J. Am. Chem. Soc. 134 (2012) 12219-12229. [PMID: 22741921]
Accepted name: 2-epi-valiolone synthase
Reaction: D-sedoheptulose 7-phosphate = 2-epi-valiolone + phosphate
For diagram of reaction click here.
Glossary: 2-epi-valiolone = (2S,3S,4S,5S)-2,3,4,5-tetrahydroxy-5-(hydroxymethyl)cyclohexan-1-one
Systematic name: D-sedoheptulose-7-phosphate phosphate-lyase (cyclizing; 2-epi-valiolone-forming)
Comments: The enzyme, characterized from the bacteria Actinosynnema mirum and Stigmatella aurantiaca DW4/3-1, produces 2-epi-valiolone, which is believed to function as a precursor in aminocyclitol biosynthesis. It requires a divalent metal ion (Zn2+ or Co2+) and an NAD+ cofactor, which is transiently reduced during the reaction. cf. EC 4.2.3.152, 2-epi-5-epi-valiolone synthase and EC 4.2.3.154, desmethyl-4-deoxygadusol synthase.
Links to other databases: BRENDA, EXPASY, KEGG, MetaCyc, CAS registry number:
References:
1. Asamizu, S., Xie, P., Brumsted, C.J., Flatt, P.M. and Mahmud, T. Evolutionary divergence of sedoheptulose 7-phosphate cyclases leads to several distinct cyclic products. J. Am. Chem. Soc. 134 (2012) 12219-12229. [PMID: 22741921]
Accepted name: hydroxysqualene synthase
Reaction: presqualene diphosphate + H2O = hydroxysqualene + diphosphate
For diagram of reaction click here.
Glossary: hydroxysqualene = (6E,10E,12R,14E,18E)-2,6,10,15,19,23-hexamethyltetracosa-2,6,10,14,18,22-hexaen-12-ol
Other name(s): hpnC (gene name)
Systematic name: presqualene diphosphate diphosphate-lyase (adding water; hydroxyasqualene-forming)
Comments: This enzyme, isolated from the bacteria Rhodopseudomonas palustris and Zymomonas mobilis, participates, along with EC 2.5.1.103, presqualene diphosphate synthase, and EC 1.17.8.1, hydroxysqualene dehydroxylase, in the conversion of all-trans-farnesyl diphosphate to squalene. Eukaryotes achieve the same goal in a single step, catalysed by EC 2.5.1.21, squalene synthase.
Links to other databases: BRENDA, EXPASY, KEGG, MetaCyc, CAS registry number:
References:
1. Pan, J.J., Solbiati, J.O., Ramamoorthy, G., Hillerich, B.S., Seidel, R.D., Cronan, J.E., Almo, S.C. and Poulter, C.D. Biosynthesis of squalene from farnesyl diphosphate in bacteria: three steps catalyzed by three enzymes. ACS Cent Sci 1 (2015) 77-82. [PMID: 26258173]
Accepted name: (+)-isoafricanol synthase
Reaction: (2E,6E)-farnesyl diphosphate + H2O = (+)-isoafricanol + diphosphate
For diagram of reaction click here.
Glossary: (+)-isoafricanol = (1aS,4aR,5R,7aS,7bR)-3,3,5,7b-tetramethyldecahydro-4aH-cyclopropa[e]azulen-4a-ol
Systematic name: (2E,6E)-farnesyl-diphosphate diphosphate-lyase [cyclizing, (+)-isoafricanol-forming]
Comments: (+)-Isoafricanol is a sesquiterpene alcohol. Its synthesis has been shown to occur in the bacteria Streptomyces violaceusniger and Streptomyces malaysiensis.
Links to other databases: BRENDA, EXPASY, KEGG, MetaCyc, PDB, CAS registry number:
References:
1. Riclea, R., Citron, C.A., Rinkel, J. and Dickschat, J.S. Identification of isoafricanol and its terpene cyclase in Streptomyces violaceusniger using CLSA-NMR. Chem. Commun. (Camb.) 50 (2014) 4228-4230. [PMID: 24626486]
2. Rabe, P., Samborskyy, M., Leadlay, P.F. and Dickschat, J.S. Isoafricanol synthase from Streptomyces malaysiensis. Org. Biomol. Chem. 15 (2017) 2353-2358. [PMID: 28247907]
Accepted name: (–)-spiroviolene synthase
Reaction: geranylgeranyl diphosphate = (–)-spiroviolene + diphosphate
For diagram of reaction click here and mechanism click here.
Glossary: (–)-spiroviolene = (2R,3a'S,3b'R,5S,6a'R)-2,4',4',5,6a'-pentamethyl-2',3',3a',3b',4',5',6',6a'-octahydrospiro[cyclopentane-1,1'-cyclopenta[a]pentalene]
Systematic name: geranylgeranyl-diphosphate diphosphate-lyase [cyclizing, (–)-spiroviolene-forming]
Comments: The enzyme, which forms the diterpene (–)-spiroviolene, has been characterized from the bacterium Streptomyces violens.
Links to other databases: BRENDA, EXPASY, KEGG, MetaCyc, PDB, CAS registry number:
References:
1. Rabe, P., Rinkel, J., Dolja, E., Schmitz, T., Nubbemeyer, B., Luu, T.H. and Dickschat, J.S. Mechanistic investigations of two bacterial diterpene cyclases: spiroviolene synthase and tsukubadiene synthase. Angew. Chem. Int. Ed. Engl. 56 (2017) 2776-2779. [PMID: 28146322]
2. Xu, H. and Dickschat, J.S. Revision of the cyclisation mechanism for the diterpene spiroviolene and investigations of its mass spectrometric fragmentation. Chembiochem 22 (2021) 850–854. [PMID: 33084237]
Accepted name: tsukubadiene synthase
Reaction: geranylgeranyl diphosphate = tsukubadiene + diphosphate
For diagram of reaction click here and mechanism click here.
Glossary: tsukubadiene = (1S,3aS,5Z,7aS,10aR,11Z)-1,5,8,8,10a-pentamethyl-2,3,3a,4,7,7a,8,9,10,10a-decahydro-1H-dicyclopenta[a,d][9]annulene
Systematic name: geranylgeranyl-diphosphate diphosphate-lyase (cyclizing, tsukubadiene-forming)
Comments: The synthesis of the diterpene tsukubadiene has been shown to occur in the Actinobacterium Streptomyces tsukubaensis.
Links to other databases: BRENDA, EXPASY, KEGG, MetaCyc, CAS registry number:
References:
1. Yamada, Y., Arima, S., Nagamitsu, T., Johmoto, K., Uekusa, H., Eguchi, T., Shin-ya, K., Cane, D.E. and Ikeda, H. Novel terpenes generated by heterologous expression of bacterial terpene synthase genes in an engineered Streptomyces host. J. Antibiot. (Tokyo) 68 (2015) 385-394. [PMID: 25605043]
2. Rabe, P., Rinkel, J., Dolja, E., Schmitz, T., Nubbemeyer, B., Luu, T.H. and Dickschat, J.S. Mechanistic investigations of two bacterial diterpene cyclases: spiroviolene synthase and tsukubadiene synthase. Angew. Chem. Int. Ed. Engl. 56 (2017) 2776-2779. [PMID: 28146322]
Accepted name: (2S,3R,6S,9S)-(–)-protoillud-7-ene synthase
Reaction: (2E,6E)-farnesyl diphosphate = (2S,3R,6S,9S)-(–)-protoillud-7-ene + diphosphate
For diagram of reaction click here and mechanism click here.
Glossary: (2S,3R,6S,9S)-(–)-protoillud-7-ene = (2aS,4aS,7aS,7bR)-3,6,6,7b-tetramethyl-2,2a,4a,5,6,7,7a,7b-octahydro-1H-cyclobuta[e]indene
pentalenene = (3aS,5aS,8aR)-1,4,7,7-tetramethyl-1,2,3,3a,5a,6,7,8-octahydrocyclopenta[c]pentalene
Other name(s): TPS6 (gene name)
Systematic name: (2E,6E)-farnesyl-diphosphate diphosphate-lyase [cyclizing, (2S,3R,6S,9S)-(–)-protoillud-7-ene-forming]
Comments: The enzyme has been described from the slime-mould Dictyostelium discoideum. It is specific for (2E,6E)-farnesyl diphosphate. While the major product is the sequiterpene (2S,3R,6S,9S)-(–)-protoillud-7-ene, traces of pentalenene are also formed.
Links to other databases: BRENDA, EXPASY, KEGG, MetaCyc, CAS registry number:
References:
1. Chen, X., Kollner, T.G., Jia, Q., Norris, A., Santhanam, B., Rabe, P., Dickschat, J.S., Shaulsky, G., Gershenzon, J. and Chen, F. Terpene synthase genes in eukaryotes beyond plants and fungi: occurrence in social amoebae. Proc. Natl Acad. Sci. USA 113 (2016) 12132-12137. [PMID: 27790999]
2. Rabe, P., Rinkel, J., Nubbemeyer, B., Kollner, T.G., Chen, F. and Dickschat, J.S. Terpene cyclases from social Amoebae. Angew. Chem. Int. Ed. Engl. 55 (2016) 15420-15423. [PMID: 27862766]
= Accepted name: (3S)-(+)-asterisca-2(9),6-diene synthase
Reaction: (2E,6E)-farnesyl diphosphate = (3S)-(+)-asterisca-2(9),6-diene + diphosphate
For diagram of reaction click here
Glossary: (3S)-(+)-asterisca-2(9),6-diene = (4S,7Z)-2,2,4,7-tetramethyl-2,3,4,5,6,9-hexahydro-1H-cyclopenta[8]annulene
Other name(s): TPS2 (gene name)
Systematic name: (2E,6E)-farnesyl-diphosphate diphosphate-lyase [cyclizing, (3S)-(+)-asterisca-2(9),6-diene-forming]
Comments: The sequiterpene (3S)-(+)-asterisca-2(9),6-diene has been shown to be synthezised in the slime-mould Dictyostelium discoideum. The enzyme is specific for (2E,6E)-farnesyl diphosphate.
Links to other databases: BRENDA, EXPASY, KEGG, MetaCyc, CAS registry number:
References:
1. Chen, X., Kollner, T.G., Jia, Q., Norris, A., Santhanam, B., Rabe, P., Dickschat, J.S., Shaulsky, G., Gershenzon, J. and Chen, F. Terpene synthase genes in eukaryotes beyond plants and fungi: occurrence in social amoebae. Proc. Natl Acad. Sci. USA 113 (2016) 12132-12137. [PMID: 27790999]
2. Rabe, P., Rinkel, J., Nubbemeyer, B., Kollner, T.G., Chen, F. and Dickschat, J.S. Terpene cyclases from social Amoebae. Angew. Chem. Int. Ed. Engl. 55 (2016) 15420-15423. [PMID: 27862766]
Accepted name: (–)-α-amorphene synthase
Reaction: (2E,6E)-farnesyl diphosphate = (–)-α-amorphene + diphosphate
For diagram of reaction click here
Glossary: (–)-α-amorphene = (1S,4aR,8aS)-4,7-dimethyl-1-(propan-2-yl)-1,2,4a,5,6,8a-hexahydronaphthalene
Systematic name: (2E,6E)-farnesyl-diphosphate diphosphate-lyase [cyclizing, (–)-α-amorphene-forming]
Comments: The enzyme, found in the bacterium Streptomyces viridochromogenes, is specific for (2E,6E)-farnesyl diphosphate and produces only (–)-α-amorphene.
Links to other databases: BRENDA, EXPASY, KEGG, MetaCyc, CAS registry number:
References:
1. Rabe, P. and Dickschat, J.S. Rapid chemical characterization of bacterial terpene synthases. Angew. Chem. Int. Ed. Engl. 52 (2013) 1810-1812. [PMID: 23307484]
2. Rinkel, J., Rabe, P., Garbeva, P. and Dickschat, J.S. Lessons from 1,3-hydride shifts in sesquiterpene cyclizations. Angew. Chem. Int. Ed. Engl. 55 (2016) 13593-13596. [PMID: 27666571]
3. Rabe, P., Schmitz, T. and Dickschat, J.S. Mechanistic investigations on six bacterial terpene cyclases. Beilstein J. Org. Chem. 12 (2016) 1839-1850. [PMID: 27829890]
Accepted name: (+)-corvol ether B synthase
Reaction: (2E,6E)-farnesyl diphosphate + H2O = (+)-corvol ether B + diphosphate
For diagram of reaction click here
Glossary: (+)-corvol ether B = (1S,3R,5aR,6S,8aR)-3,6-dimethyl-1-(propan-2-yl)hexahydro-1H,3H-3,8a-methanocyclopenta[c]oxepine
Systematic name: (2E,6E)-farnesyl-diphosphate diphosphate-lyase [cyclizing, (+)-corvol ether B-forming]
Comments: The enzyme, which forms the sesquiterpene (+)-corvol ether B, has been reported from the bacterium Kitasatospora setae.
Links to other databases: BRENDA, EXPASY, KEGG, MetaCyc, CAS registry number:
References:
1. Rabe, P., Pahirulzaman, K.A. and Dickschat, J.S. Structures and biosynthesis of corvol ethers —sesquiterpenes from the actinomycete Kitasatospora setae. Angew. Chem. Int. Ed. Engl. 54 (2015) 6041-6045. [PMID: 25809275]
2. Rabe, P., Janusko, A., Goldfuss, B. and Dickschat, J.S. Experimental and theoretical studies on corvol ether biosynthesis. Chembiochem. 17 (2016) 146-149. [PMID: 26635093]
3. Rinkel, J., Rabe, P., Garbeva, P. and Dickschat, J.S. Lessons from 1,3-hydride shifts in sesquiterpene cyclizations. Angew. Chem. Int. Ed. Engl. 55 (2016) 13593-13596. [PMID: 27666571]
Accepted name: (+)-eremophilene synthase
Reaction: (2E,6E)-farnesyl diphosphate = (+)-eremophilene + diphosphate
For diagram of reaction click here
Glossary: (+)-eremophilene = (3S,4aS,5R)-4a,5-dimethyl-3-(prop-1-en-2-yl)-1,2,3,4,4a,5,6,7-octahydronaphthalene
Other name(s): STC3 (gene name); geoA (gene name)
Systematic name: (2E,6E)-farnesyl-diphosphate diphosphate-lyase [cyclizing, (+)-eremophilene-forming]
Comments: The enzyme has been identified in the myxobacterium Sorangium cellulosum and in the fungus Fusarium fujikuroi.
Links to other databases: BRENDA, EXPASY, KEGG, MetaCyc, CAS registry number:
References:
1. Schifrin, A., Ly, T.T., Gunnewich, N., Zapp, J., Thiel, V., Schulz, S., Hannemann, F., Khatri, Y. and Bernhardt, R. Characterization of the gene cluster CYP264B1-geoA from Sorangium cellulosum So ce56: biosynthesis of (+)-eremophilene and its hydroxylation. Chembiochem 16 (2015) 337-344. [PMID: 25504914]
2. Burkhardt, I., Siemon, T., Henrot, M., Studt, L., Rosler, S., Tudzynski, B., Christmann, M. and Dickschat, J.S. Mechanistic characterisation of two sesquiterpene cyclases from the plant pathogenic fungus Fusarium fujikuroi. Angew. Chem. Int. Ed. Engl. 55 (2016) 8748-8751. [PMID: 27294564]
Accepted name: (1R,4R,5S)-(–)-guaia-6,10(14)-diene synthase
Reaction: (2E,6E)-farnesyl diphosphate = (1R,4R,5S)-(–)-guaia-6,10(14)-diene + diphosphate
For diagram of reaction click here
Glossary: (1R,4R,5S)-(–)-guaia-6,10(14)-diene = (1R)-1-methyl-4-methylidene-7-(propan-2-yl)-1,2,3,3a,4,5,6,8a-octahydroazulene = (1R)-7-isopropyl-1-methyl-4-methylene-1,2,3,3a,4,5,6,8a-octahydroazulene
Other name(s): STC5 (gene name)
Systematic name: (2E,6E)-farnesyl-diphosphate diphosphate-lyase [cyclizing, (1R,4R,5S)-(–)-guaia-6,10(14)-diene-forming]
Comments: The original enzyme (STC5) from the fungus Fusarium fujikuroi is inactive because of a critically naturally occuring mutation that leads to an asparagine to lysine exchange in the NSE (Asn-Ser-Glu) triad, a highly conserved motif of type I terpene cyclases. Sequence correction by site-directed mutagenesis (K288N) restores activity.
Links to other databases: BRENDA, EXPASY, KEGG, MetaCyc, CAS registry number:
References:
1. Burkhardt, I., Siemon, T., Henrot, M., Studt, L., Rosler, S., Tudzynski, B., Christmann, M. and Dickschat, J.S. Mechanistic characterisation of two sesquiterpene cyclases from the plant pathogenic fungus Fusarium fujikuroi. Angew. Chem. Int. Ed. Engl. 55 (2016) 8748-8751. [PMID: 27294564]
Accepted name: (+)-(1E,4E,6S,7R)-germacra-1(10),4-dien-6-ol synthase
Reaction: (2E,6E)-farnesyl diphosphate + H2O = (+)-(1E,4E,6S,7R)-germacra-1(10),4-dien-6-ol + diphosphate
For diagram of reaction click here
Glossary: (+)-(1E,4E,6S,7R)-germacra-1(10),4-dien-6-ol = (1S,2E,6E,10R)-3,7-dimethyl-10-(propan-2-yl)cyclodeca-2,6-dien-1-ol
Systematic name: (2E,6E)-farnesyl-diphosphate diphosphate-lyase [cyclizing, (+)-(1E,4E,6S,7R)-germacra-1(10),4-dien-6-ol-forming]
Comments: The enzyme has been identified in the bacterium Streptomyces pratensis. It is specific for (2E,6E)-farnesyl diphosphate.
Links to other databases: BRENDA, EXPASY, KEGG, MetaCyc, CAS registry number:
References:
1. Rabe, P., Barra, L., Rinkel, J., Riclea, R., Citron, C.A., Klapschinski, T.A., Janusko, A. and Dickschat, J.S. Conformational analysis, thermal rearrangement, and EI-MS fragmentation mechanism of ((1(10)E,4E,6S,7R)-germacradien-6-ol by 13C-labeling experiments. Angew. Chem. Int. Ed. Engl. 54 (2015) 13448-13451. [PMID: 26361082]
Accepted name: dolabella-3,7-dien-18-ol synthase
Reaction: geranylgeranyl diphosphate + H2O = (3E,7E)-dolabella-3,7-dien-18-ol + diphosphate
For diagram of reaction click here
Glossary: (3E,7E)-dolabella-3,7-dien-18-ol = 2-[(1R,3aR,5E,9E,12aR)-3a,6,10-trimethyl-1,2,3,3a,4,7,8,11,12,12a-decahydrocyclopenta[11]annulen-1-yl]propan-2-ol
Other name(s): TPS20 (gene name)
Systematic name: geranylgeranyl-diphosphate diphosphate-lyase [cyclizing, (3E,7E)-dolabella-3,7-dien-18-ol-forming]
Comments: Isolated from an ecotype of the plant Arabidopsis thaliana from Cape Verde Islands. The enzyme also gives (3E,7E)-dolathalia-3,7,11-triene and traces of other terpenoids. cf. EC 4.2.3.168 dolathalia-3,7,11-triene synthase.
Links to other databases: BRENDA, EXPASY, KEGG, MetaCyc, CAS registry number:
References:
1. Wang, Q., Jia, M., Huh, J.H., Muchlinski, A., Peters, R.J. and Tholl, D. Identification of a dolabellane type diterpene synthase and other root-expressed diterpene synthases in Arabidopsis. Front. Plant Sci. 7 (2016) 1761. [PMID: 27933080]
Accepted name: dolathalia-3,7,11-triene synthase
Reaction: geranylgeranyl diphosphate = (3E,7E)-dolathalia-3,7,11-triene + diphosphate
For diagram of reaction click here
Glossary: (3E,7E)-dolathalia-3,7,11-triene = (7E,11E)-3,3,7,11,13a-pentamethy1-2,3,5,6,9,10,13,13a-octahydro-1H-benzo[11]annulene
Other name(s): TPS20 (gene name)
Systematic name: geranylgeranyl-diphosphate diphosphate-lyase [cyclizing, (3E,7E)-dolathalia-3,7,11-triene-forming]
Comments: Isolated from an ecotype of the plant Arabidopsis thaliana from Cape Verde Islands. The enzyme also gives (3E,7E)-dolabella-3,7-dien-18-ol and traces of other terpenoids. cf. EC 4.2.3.167 dolabella-3,7-dien-18-ol synthase.
Links to other databases: BRENDA, EXPASY, KEGG, MetaCyc, CAS registry number:
References:
1. Wang, Q., Jia, M., Huh, J.H., Muchlinski, A., Peters, R.J. and Tholl, D. Identification of a dolabellane type diterpene synthase and other root-expressed diterpene synthases in Arabidopsis. Front. Plant Sci. 7 (2016) 1761. [PMID: 27933080]
Accepted name: 7-epi-α-eudesmol synthase
Reaction: (2E,6E)-farnesyl diphosphate + H2O = 7-epi-α-eudesmol + diphosphate
For diagram of reaction click here
Glossary: 7-epi-α-eudesmol = 2-[(2S,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 (cyclizing, 7-epi-α-eudesmol-forming)
Comments: The enzyme, found in the bacterium Streptomyces viridochromogenes, is specific for (2E,6E)-farnesyl diphosphate.
Links to other databases: BRENDA, EXPASY, KEGG, MetaCyc, CAS registry number:
References:
1. Rabe, P., Schmitz, T. and Dickschat, J.S. Mechanistic investigations on six bacterial terpene cyclases. Beilstein J. Org. Chem. 12 (2016) 1839-1850. [PMID: 27829890]
Accepted name: 4-epi-cubebol synthase
Reaction: (2E,6E)-farnesyl diphosphate + H2O = 4-epi-cubebol + diphosphate
For diagram of reaction click here
Glossary: 4-epi-cubebol = (3S,3aS,3bR,4S,7S,7aS)-4-(2-hydroxypropan-2-yl)-7-methyloctahydro-1H-cyclopenta[1,3]cyclopropa[1,2]benzen-3-ol
Systematic name: (2E,6E)-farnesyl-diphosphate diphosphate-lyase (cyclizing, 4-epi-cubebol-forming)
Comments: The enzyme, found in the bacterium Streptosporangium roseum, is specific for (2E,6E)-farnesyl diphosphate.
Links to other databases: BRENDA, EXPASY, KEGG, MetaCyc, CAS registry number:
References:
1. Rabe, P., Schmitz, T. and Dickschat, J.S. Mechanistic investigations on six bacterial terpene cyclases. Beilstein J. Org. Chem. 12 (2016) 1839-1850. [PMID: 27829890]
Accepted name: (+)-corvol ether A synthase
Reaction: (2E,6E)-farnesyl diphosphate + H2O = (+)-corvol ether A + diphosphate
For diagram of reaction click here
Glossary: (+)-corvol ether A = (1R,4S,4aR,7R,8aR)-4,7-dimethyl-1-(propan-2-yl)decahydro-1,7-epoxynaphthalene
Systematic name: (2E,6E)-farnesyl-diphosphate diphosphate-lyase [cyclizing, (+)-corvol ether A-forming]
Comments: The enzyme, which forms the sesquiterpene (+)-corvol ether A, has been reported from the bacterium Kitasatospora setae.
Links to other databases: BRENDA, EXPASY, KEGG, MetaCyc, CAS registry number:
References:
1. Rabe, P., Pahirulzaman, K.A. and Dickschat, J.S. Structures and biosynthesis of corvol ethers —sesquiterpenes from the actinomycete Kitasatospora setae. Angew. Chem. Int. Ed. Engl. 54 (2015) 6041-6045. [PMID: 25809275]
2. Rabe, P., Janusko, A., Goldfuss, B. and Dickschat, J.S. Experimental and theoretical studies on corvol ether biosynthesis. Chembiochem. 17 (2016) 146-149. [PMID: 26635093]
3. Rinkel, J., Rabe, P., Garbeva, P. and Dickschat, J.S. Lessons from 1,3-hydride shifts in sesquiterpene cyclizations. Angew. Chem. Int. Ed. Engl. 55 (2016) 13593-13596. [PMID: 27666571]
Accepted name: 10-epi-juneol synthase
Reaction: (2E,6E)-farnesyl diphosphate + H2O = 10-epi-juneol + diphosphate
For diagram of reaction click here
Glossary: 10-epi-juneol = 10α-eudesm-4(14)-en-6α-ol
Systematic name: (2E,6E)-farnesyl-diphosphate diphosphate-lyase (cyclizing, 10-epi-juneol-forming)
Comments: Isolated from the plant Inula hupehensis. The enzyme also gives gives
Links to other databases: BRENDA, EXPASY, KEGG, MetaCyc, CAS registry number:
References:
1. Gou, J.B., Li, Z.Q., Li, C.F., Chen, F.F., Lv, S.Y. and Zhang, Y.S. Molecular cloning and functional analysis of a 10-epi-junenol synthase from Inula hupehensis. Plant Physiol. Biochem. 106 (2016) 288-294. [PMID: 27231873]
Accepted name:
Reaction: (2E,6E)-farnesyl diphosphate + H2O =
For diagram of reaction click here
Glossary:
Systematic name: (2E,6E)-farnesyl-diphosphate diphosphate-lyase (cyclizing,
Comments: Isolated from the plant Inula hupehensis. The enzyme also gives 10-epi-juneol and traces of other terpenoids, see EC 4.2.3.172, 10-epi-juneol synthase. It has also been isolated from the plants maize (Zea mays) and lavender (Lavandula angustifolia).
Links to other databases: BRENDA, EXPASY, KEGG, MetaCyc, CAS registry number:
References:
1. Gou, J.B., Li, Z.Q., Li, C.F., Chen, F.F., Lv, S.Y. and Zhang, Y.S. Molecular cloning and functional analysis of a 10-epi-junenol synthase from Inula hupehensis. Plant Physiol. Biochem. 106 (2016) 288-294. [PMID: 27231873]
2. Jullien, F., Moja, S., Bony, A., Legrand, S., Petit, C., Benabdelkader, T., Poirot, K., Fiorucci, S., Guitton, Y., Nicole, F., Baudino, S. and Magnard, J.L. Isolation and functional characterization of a
3. Ren, F., Mao, H., Liang, J., Liu, J., Shu, K. and Wang, Q. Functional characterization of ZmTPS7 reveals a maize
Accepted name: (2E,6E)-hedycaryol synthase
Reaction: (2E,6E)-farnesyl diphosphate + H2O = (2E,6E)-hedycaryol + diphosphate
For diagram of reaction click here
Glossary: (2E,6E)-hedycaryol = (1E,4E,7S)-germacra-1(10),4-dien-11-ol
Systematic name: (2E,6E)-farnesyl-diphosphate diphosphate-lyase [cyclizing, (2E,6E)-hedycaryol-forming]
Comments: Isolated from the plant Camellia brevistyla. See also EC 4.2.3.187, (2Z,6E)-hedycaryol synthase.
Links to other databases: BRENDA, EXPASY, KEGG, MetaCyc, CAS registry number:
References:
1. Hattan, J., Shindo, K., Ito, T., Shibuya, Y., Watanabe, A., Tagaki, C., Ohno, F., Sasaki, T., Ishii, J., Kondo, A. and Misawa, N. Identification of a novel hedycaryol synthase gene isolated from Camellia brevistyla flowers and floral scent of Camellia cultivars. Planta 243 (2016) 959-972. [PMID: 26744017]
Accepted name: 10-epi-cubebol synthase
Reaction: (2E,6E)-farnesyl diphosphate + H2O = 10-epi-cubebol + diphosphate
For diagram of reaction click here
Other name(s): sce6369
Systematic name: (2E,6E)-farnesyl-diphosphate diphosphate-lyase (cyclizing, 10-epi-cubebol-forming)
Comments: Isolated from the bacterium Sorangium cellulosum So ce56. The enzyme is also responsible for the formation of trace amounts of many other sesquiterpenes, mainly cadinanes and cubebanes.
Links to other databases: BRENDA, EXPASY, KEGG, MetaCyc, PDB, CAS registry number:
References:
1. Schifrin, A., Khatri, Y., Kirsch, P., Thiel, V., Schulz, S. and Bernhardt, R. A single terpene synthase is responsible for a wide variety of sesquiterpenes in Sorangium cellulosum Soce56. Org. Biomol. Chem. 14 (2016) 3385-3393. [PMID: 26947062]
Accepted name: sesterfisherol synthase
Reaction: (2E,6E,10E,14E)-geranylfarnesyl diphosphate + H2O = sesterfisherol + diphosphate
For diagram of reaction click here Glossary: sesterfisherol = (3R,3aS,6S,6aR,7aR,10R,10aS,11aR)-3,6,7a,12-tetramethyl-10-(propan-2-yl)-2,3,3a,4,5,6,6a,7,7a,8,9,10,10a,11-tetradecahydrocyclopenta[4,5]cycloocta[f]inden-11a(1H)-ol
Other name(s): NfSS
Systematic name: (2E,6E,10E,14E)-geranylfarnesyl-diphosphate diphosphate-lyase (cyclizing, sesterfisherol-forming)
Comments: Isolated from the fungus Neosartorya fischeri.
Links to other databases: BRENDA, EXPASY, KEGG, MetaCyc, CAS registry number:
References:
1. Ye, Y., Minami, A., Mandi, A., Liu, C., Taniguchi, T., Kuzuyama, T., Monde, K., Gomi, K. and Oikawa, H. Genome mining for sesterterpenes using bifunctional terpene synthases reveals a unified intermediate of di/sesterterpenes. J. Am. Chem. Soc. 137 (2015) 11846-11853. [PMID: 26332841]
Accepted name: β-thujene synthase
Reaction: geranyl diphosphate = β-thujene + diphosphate
For diagram of reaction click here
Other name(s): CoTPS1
Systematic name: geranyl-diphosphate diphosphate-lyase (cyclizing, β-thujene-forming)
Comments: Isolated from the plant Cananga odorata var. fruticosa (ylang ylang). The enzyme forms roughly equal proportions of β-thujene, sabinene, β-pinene and α-terpinene see EC 4.2.3.109/EC 4.2.3.110 sabinene synthase, EC 4.2.3.120/EC 4.2.3.122 β-pinene synthase, EC 4.2.3.115 α-terpinene synthase.
Links to other databases: BRENDA, EXPASY, KEGG, MetaCyc, CAS registry number:
References:
1. Jin, J., Kim, M.J., Dhandapani, S., Tjhang, J.G., Yin, J.L., Wong, L., Sarojam, R., Chua, N.H. and Jang, I.C. The floral transcriptome of ylang ylang (Cananga odorata var. fruticosa) uncovers biosynthetic pathways for volatile organic compounds and a multifunctional and novel sesquiterpene synthase. J. Exp. Bot. 66 (2015) 3959-3975. [PMID: 25956881]
Accepted name: stellata-2,6,19-triene synthase
Reaction: (2E,6E,10E,14E)-geranylfarnesyl diphosphate = stellata-2,6,19-triene + diphosphate
For diagram of reaction click here Glossary: stellata-2,6,19-triene = (3S,3aR,5aR,7E,11E,14aR,14bR)-5a,8,12,14b-tetramethyl-3-(prop-1-en-2-yl)-1,2,3,3a,4,5,5a,6,9,10,13,14,14a,14b-tetradecahydrocycloundeca[e]indene
Systematic name: (2E,6E,10E,14E)-geranylfarnesyl-diphosphate diphosphate-lyase (cylizing, stellata-2,6,19-triene-forming)
Comments: Isolated from the fungus Aspergillus stellatus.
Links to other databases: BRENDA, EXPASY, KEGG, MetaCyc, CAS registry number:
References:
1. Matsuda, Y., Mitsuhashi, T., Quan, Z. and Abe, I. Molecular basis for stellatic acid biosynthesis: a genome mining approach for discovery of sesterterpene synthases. Org. Lett. 17 (2015) 4644-4647. [PMID: 26351860]
Accepted name: guaia-4,6-diene synthase
Reaction: (2E,6E)-farnesyl diphosphate = guaia-4,6-diene + diphosphate
For diagram of reaction click here
Other name(s): XsTPS2
Systematic name: (2E,6E)-farnesyl-diphosphate diphosphate-lyase (cyclizing, guaia-4,6-diene-forming)
Comments: Isolated from the plant Xanthium strumarium (rough cocklebur).
Links to other databases: BRENDA, EXPASY, KEGG, MetaCyc, CAS registry number:
References:
1. Li, Y., Chen, F., Li, Z., Li, C. and Zhang, Y. Identification and functional characterization of sesquiterpene synthases from Xanthium strumarium. Plant Cell Physiol 57 (2016) 630-641. [PMID: 26858282]
Accepted name: pseudolaratriene synthase
Reaction: geranylgeranyl diphosphate = pseudolaratriene + diphosphate
For diagram of reaction click here and mechanism click here.
Glossary: pseudolaradiene = (1RS,3aSR,8aRS)-3a,6-dimethyl-1-(6-methylhepta-2,5-dien-2-yl)-1,2,3,3a,4,7,8,8a-octahydrohydroazulene
Other name(s): PxaTPS8
Systematic name: geranylgeranyl-diphosphate diphosphate-lyase (cyclizing, pseudolaradiene-forming)
Comments: Isolated from the plant Pseudolarix amabilis (golden larch). The product is oxidized to pseudolaric acid B, a microtubule-destabilizing agent.
Links to other databases: BRENDA, EXPASY, KEGG, MetaCyc, CAS registry number:
References:
1. Mafu, S., Karunanithi, P.S., Palazzo, T.A., Harrod, B.L., Rodriguez, S.M., Mollhoff, I.N., O'Brien, T.E., Tong, S., Fiehn, O., Tantillo, D.J., Bohlmann, J. and Zerbe, P. Biosynthesis of the microtubule-destabilizing diterpene pseudolaric acid B from golden larch involves an unusual diterpene synthase. Proc. Natl Acad. Sci. USA 114 (2017) 974-979. [PMID: 28096378]
Accepted name: selina-4(15),7(11)-diene synthase
Reaction: (2E,6E)-farnesyl diphosphate = selina-4(15),7(11)-diene + diphosphate
For diagram of reaction click here
Other name(s): SdS
Systematic name: (2E,6E)-farnesyl-diphosphate diphosphate-lyase (cyclizing, selina-4(15),7(11)-diene-forming)
Comments: Isolated from the bacteria Streptomyces pristinaespiralis and S. somaliensis.
Links to other databases: BRENDA, EXPASY, KEGG, MetaCyc, PDB, CAS registry number:
References:
1. Rabe, P. and Dickschat, J.S. Rapid chemical characterization of bacterial terpene synthases. Angew. Chem. Int. Ed. Engl. 52 (2013) 1810-1812. [PMID: 23307484]
2. Baer, P., Rabe, P., Fischer, K., Citron, C.A., Klapschinski, T.A., Groll, M. and Dickschat, J.S. Induced-fit mechanism in class I terpene cyclases. Angew. Chem. Int. Ed. Engl. 53 (2014) 7652-7656. [PMID: 24890698]
Accepted name: pristinol synthase
Reaction: (2E,6E)-farnesyl diphosphate + H2O = (+)-(2S,3R,9R)-pristinol + diphosphate
For diagram of reaction click here and mechanism click here.
Glossary: (+)-(2S,3R,9R)-pristinol = (1R,6R,9aS)-1,4,8,8-tetramethyl-2,3,5,6,7,8,9,9a-octahydro-1H-cyclopenta[8]annulen-6-ol
Systematic name: (2E,6E)-farnesyl-diphosphate diphosphate-lyase [cyclizing, (+)-(2S,3R,9R)-pristinol-forming]
Comments: Isolated from the bacterium Streptomyces pristinaespiralis.
Links to other databases: BRENDA, EXPASY, KEGG, MetaCyc, PDB, CAS registry number:
References:
1. Klapschinski, T.A., Rabe, P. and Dickschat, J.S. Pristinol, a sesquiterpene alcohol with an unusual skeleton from Streptomyces pristinaespiralis. Angew. Chem. Int. Ed. Engl. 55 (2016) 10141-10144. [PMID: 27403888]
Accepted name: nezukol synthase
Reaction: (+)-copalyl diphosphate + H2O = nezukol + diphosphate
For diagram of reaction click here
Glossary: (+)-copalyl diphosphate = (2E)-3-methyl-5-[(1S,4aS,8aS)-5,5,8a-trimethyl-2-methylidenedecahydronaphthalen-1-yl]pent-2-en-1-yl trihydrogen diphosphate
nezukol = pimar-15-en-8-ol
Other name(s): TPS2
Systematic name: (+)-copalyl-diphosphate diphosphate-lyase (cyclizing, nezukol-forming)
Comments: Isolated from the plant Isodon rubescens.
Links to other databases: BRENDA, EXPASY, KEGG, MetaCyc, CAS registry number:
References:
1. Pelot, K.A., Hagelthorn, D.M., Addison, J.B. and Zerbe, P. Biosynthesis of the oxygenated diterpene nezukol in the medicinal plant Isodon rubescens is catalyzed by a pair of diterpene synthases. PLoS One 12 (2017) e0176507. [PMID: 28445526]
Accepted name: 5-hydroxy-α-gurjunene synthase
Reaction: (2E,6E)-farnesyl diphosphate + H2O = 5-hydroxy-α-gurjunene + diphosphate
For diagram of reaction click here
Other name(s): MpMTPSL4
Systematic name: (2E,6E)-farnesyl-diphosphate diphosphate-lyase (cyclizing, 5-hydroxy-α-gurjunene-forming)
Comments: Isolated from the liverwort Marchantia polymorpha.
Links to other databases: BRENDA, EXPASY, KEGG, MetaCyc, CAS registry number:
References:
1. Kumar, S., Kempinski, C., Zhuang, X., Norris, A., Mafu, S., Zi, J., Bell, S.A., Nybo, S.E., Kinison, S.E., Jiang, Z., Goklany, S., Linscott, K.B., Chen, X., Jia, Q., Brown, S.D., Bowman, J.L., Babbitt, P.C., Peters, R.J., Chen, F. and Chappell, J. Molecular diversity of terpene synthases in the liverwort Marchantia polymorpha. Plant Cell 28 (2016) 2632-2650. [PMID: 27650333]
Accepted name: ent-atiserene synthase
Reaction: ent-copalyl diphosphate = ent-atiserene + diphosphate
For diagram of reaction click here and mechanism click here
Other name(s): IrKSL4
Systematic name: ent-copalyl-diphosphate diphosphate-lyase (cyclizing, ent-atiserine-forming)
Comments: Isolated from the plant Isodon rubescens and several species of Aconitum as well as species of Streptomyces.
Links to other databases: BRENDA, EXPASY, KEGG, MetaCyc, CAS registry number:
References:
1. Smanski, M.J., Yu, Z., Casper, J., Lin, S., Peterson, R.M., Chen, Y., Wendt-Pienkowski, E., Rajski, S.R. and Shen, B. Dedicated ent-kaurene and ent-atiserene synthases for platensimycin and platencin biosynthesis. Proc. Natl. Acad. Sci. USA 108 (2011) 13498–13503. [PMID: 21825154]
2. Jin, B., Cui, G., Guo, J., Tang, J., Duan, L., Lin, H., Shen, Y., Chen, T., Zhang, H. and Huang, L. Functional diversification of kaurene synthase-like genes in Isodon rubescens. Plant Physiol. 174 (2017) 943-955. [PMID: 28381502]
3. Tian, M., Jin, B., Chen, L., Ma, R., Ma, Q., Li, X., Chen, T., Guo, J., Ge, H., Zhao, X., Lai, C., Tang, J., Cui, G. and Huang, L. Functional diversity of diterpene synthases in Aconitum plants. Plant Physiol. Biochem. 202 (2023) 107968. [PMID: 37619270]
Accepted name: ent-13-epi-manoyl oxide synthase
Reaction: ent-8α-hydroxylabd-13-en-15-yl diphosphate = ent-13-epi-manoyl oxide + diphosphate
For diagram of reaction click here
Glossary: Ent-13-epi-manoyl oxide = (13R)-ent-8,13-epoxylabd-14-ene
Other name(s): SmKSL2; ent-LDPP synthase
Systematic name: ent-8α-hydroxylabd-13-en-15-yl-diphosphate diphosphate-lyase (cyclizing, ent-13-epi-manoyl-oxide-forming)
Comments: Isolated from the plant Salvia miltiorrhiza (red sage).
Links to other databases: BRENDA, EXPASY, KEGG, MetaCyc, CAS registry number:
References:
1. Cui, G., Duan, L., Jin, B., Qian, J., Xue, Z., Shen, G., Snyder, J.H., Song, J., Chen, S., Huang, L., Peters, R.J. and Qi, X. Functional divergence of diterpene syntheses in the medicinal plant Salvia miltiorrhiza. Plant Physiol. 169 (2015) 1607-1618. [PMID: 26077765]
Accepted name: (2Z,6E)-hedycaryol synthase
Reaction: (2E,6E)-farnesyl diphosphate + H2O = (2Z,6E)-hedycaryol + diphosphate
For diagram of reaction click here
Glossary: (2Z,6E)-hedycaryol = (1E,4Z,7S)-germacra-1(10),4-dien-11-ol
Other name(s): HcS
Systematic name: (2E,6E)-farnesyl-diphosphate diphosphate-lyase [cyclizing, (2Z,6E)-hedycaryol-forming]
Comments: Isolated from the bacterium Kitasatospora setae. The stereochemistry suggests the farnesyl diphosphate rearranges to nerolidyl diphosphate or an equivalent intermediate before cyclization. See also EC 4.2.3.174 (2E,6E)-hedycaryol synthase.
Links to other databases: BRENDA, EXPASY, KEGG, MetaCyc, PDB, CAS registry number:
References:
1. Baer, P., Rabe, P., Citron, C.A., de Oliveira Mann, C.C., Kaufmann, N., Groll, M. and Dickschat, J.S. Hedycaryol synthase in complex with nerolidol reveals terpene cyclase mechanism. Chembiochem 15 (2014) 213-216. [PMID: 24399794]
Accepted name: β-geranylfarnesene synthase
Reaction: (1) all-trans-geranylfarnesyl diphosphate = β-geranylfarnesene + diphosphate
(2) all-trans-hexaprenyl diphosphate = β-hexaprene + diphosphate
(3) all-trans-heptaprenyl diphosphate = β-heptaprene + diphosphate
For diagram of reaction click here or click here.
Glossary: β-geranylfarnesene = (6E,10E,14E)-7,11,15,19-tetramethyl-3-methyleneicosa-1,6,10,14,18-pentaene
Other name(s): Bcl-TS
Systematic name: all-trans-geranylfarnesyl-diphosphate diphosphate-lyase (β-geranylfarnesene-forming)
Comments: Isolated from the bacterium Bacillus clausii. The enzyme acts on a range of polyprenyl diphosphates.
Links to other databases: BRENDA, EXPASY, KEGG, MetaCyc, CAS registry number:
References:
1. Sato, T., Yamaga, H., Kashima, S., Murata, Y., Shinada, T., Nakano, C. and Hoshino, T. Identification of novel sesterterpene/triterpene synthase from Bacillus clausii. Chembiochem 14 (2013) 822-825. [PMID: 23554321]
2. Ueda, D., Yamaga, H., Murakami, M., Totsuka, Y., Shinada, T. and Sato, T. Biosynthesis of sesterterpenes, head-to-tail triterpenes, and sesquarterpenes in Bacillus clausii: identification of multifunctional enzymes and analysis of isoprenoid metabolites. Chembiochem 16 (2015) 1371-1377. [PMID: 25882275]
Accepted name: 9,13-epoxylabd-14-ene synthase
Reaction: peregrinol diphosphate = (13R)-9,13-epoxylabd-14-ene + diphosphate
For diagram of reaction click here
Glossary: peregrinol diphosphate = (13E)-9-hydroxy-8α-labd-13-en-15-yl diphosphate
Other name(s): ELS (gene name); TPS2 (gene name) (ambiguous); peregrinol-diphosphate diphosphate-lyase (9,13-epoxylabd-14-ene-forming)
Systematic name: peregrinol-diphosphate diphosphate-lyase (9,13-epoxylabd-14-ene-forming)
Comments: Isolated from the plants Marrubium vulgare (white horehound) and Vitex agnus-castus (chaste tree). Involved in marrubiin biosynthesis.
Links to other databases: BRENDA, EXPASY, KEGG, MetaCyc, CAS registry number:
References:
1. Zerbe, P., Chiang, A., Dullat, H., O'Neil-Johnson, M., Starks, C., Hamberger, B. and Bohlmann, J. Diterpene synthases of the biosynthetic system of medicinally active diterpenoids in Marrubium vulgare. Plant J. 79 (2014) 914-927. [PMID: 24990389]
2. Heskes, A.M., Sundram, T.CM., Boughton, B.A., Jensen, N.B., Hansen, N.L., Crocoll, C., Cozzi, F., Rasmussen, S., Hamberger, B., Hamberger, B., Staerk, D., Møller, B.L. and Pateraki, I. Biosynthesis of bioactive diterpenoids in the medicinal plant Vitex agnus-castus. Plant J. 93 (2018) 943-958. [PMID: 29315936]
Accepted name: manoyl oxide synthase
Reaction: (13E)-8α-hydroxylabd-13-en-15-yl diphosphate = manoyl oxide + diphosphate
For diagram of reaction click here
Glossary: (13E)-8α-hydroxylabd-13-en-15-yl diphosphate = 8-hydroxycopalyl diphosphate
manoyl oxide = (13R)-8,13-epoxylabd-14-ene
Other name(s): GrTPS6; CfTPS3; CfTPS4; MvELS
Systematic name: (13E)-8α-hydroxylabd-13-en-15-yl-diphosphate diphosphate-lyase (manoyl-oxide-forming)
Comments: Manoyl oxide is found in many plants. This enzyme has been isolated from the plants, Grindelia hirsutula (gum weed), Plectranthus barbatus (forskohlii) and Marrubium vulgare (white horehound).
Links to other databases: BRENDA, EXPASY, KEGG, MetaCyc, CAS registry number:
References:
1. Zerbe, P., Hamberger, B., Yuen, M.M., Chiang, A., Sandhu, H.K., Madilao, L.L., Nguyen, A., Hamberger, B., Bach, S.S. and Bohlmann, J. Gene discovery of modular diterpene metabolism in nonmodel systems. Plant Physiol. 162 (2013) 1073-1091. [PMID: 23613273]
2. Pateraki, I., Andersen-Ranberg, J., Hamberger, B., Heskes, A.M., Martens, H.J., Zerbe, P., Bach, S.S., Moller, B.L., Bohlmann, J. and Hamberger, B. Manoyl oxide (13R), the biosynthetic precursor of forskolin, is synthesized in specialized root cork cells in Coleus forskohlii. Plant Physiol. 164 (2014) 1222-1236. [PMID: 24481136]
3. Zerbe, P., Chiang, A., Dullat, H., O'Neil-Johnson, M., Starks, C., Hamberger, B. and Bohlmann, J. Diterpene synthases of the biosynthetic system of medicinally active diterpenoids in Marrubium vulgare. Plant J. 79 (2014) 914-927. [PMID: 24990389]
Accepted name: cycloaraneosene synthase
Reaction: geranylgeranyl diphosphate = cycloaraneosene + diphosphate
For diagram of reaction click here
Glossary: cycloaraneosene = (1R,3aR,9aS,10aR)-1,9a-dimethyl-4-methylene-7-(propan-2-yl)-1,2,3,3a,4,5,6,8,9,9a,10,10a-dodecahydrodicyclopenta[a,d][8]annulene
Other name(s): SdnA
Systematic name: geranylgeranyl-diphosphate diphosphate-lyase (cycloaraneosene-forming)
Comments: Isolated from the fungus Sordaria araneosa. Cycloaraneosene is a precursor of the antibiotic sordarin.
Links to other databases: BRENDA, EXPASY, KEGG, MetaCyc, CAS registry number:
References:
1. Kudo, F., Matsuura, Y., Hayashi, T., Fukushima, M. and Eguchi, T. Genome mining of the sordarin biosynthetic gene cluster from Sordaria araneosa Cain ATCC 36386: characterization of cycloaraneosene synthase and GDP-6-deoxyaltrose transferase. J. Antibiot. (Tokyo) 69 (2016) 541-548. [PMID: 27072286]
Accepted name: labda-7,13(16),14-triene synthase
Reaction: (13E)-labda-7,13-dienyl diphosphate = labda-7,13(16),14-triene + diphosphate
For diagram of reaction click here
Other name(s): SCLAV_p0491
Systematic name: (13E)-labda-7,13-dienyl-diphosphate diphosphate-lyase (labda-7,13(16),14-triene-forming)
Comments: Isolated from the bacterium Streptomyces clavuligerus.
Links to other databases: BRENDA, EXPASY, KEGG, MetaCyc, CAS registry number:
References:
1. Yamada, Y., Komatsu, M. and Ikeda, H. Chemical diversity of labdane-type bicyclic diterpene biosynthesis in Actinomycetales microorganisms. J. Antibiot. (Tokyo) 69 (2016) 515-523. [PMID: 26814669]
Accepted name: (12E)-labda-8(17),12,14-triene synthase
Reaction: (+)-copalyl diphosphate = (12E)-labda-8(17),12,14-triene + diphosphate
For diagram of reaction click here
Other name(s): CldD
Systematic name: (+)-copalyl-diphosphate diphosphate-lyase [(12E)-labda-8(17),12,14-triene-forming]
Comments: Isolated from the bacterium Streptomyces cyslabdanicus.
Links to other databases: BRENDA, EXPASY, KEGG, MetaCyc, PDB, CAS registry number:
References:
1. Yamada, Y., Komatsu, M. and Ikeda, H. Chemical diversity of labdane-type bicyclic diterpene biosynthesis in Actinomycetales microorganisms. J. Antibiot. (Tokyo) 69 (2016) 515-523. [PMID: 26814669]
Accepted name: (–)-drimenol synthase
Reaction: (2E,6E)-farnesyl diphosphate + H2O = (–)-drimenol + diphosphate
For diagram of reaction click here and mechanism click here.
Glossary: (–)-drimenol = drim-7-en-11-ol
Other name(s): PhDS; VoTPS3; farnesyl pyrophosphate:drimenol cyclase; drimenol cyclase; (2E,6E)-farnesyl-diphosphate diphosphohydrolase (drimenol-forming)
Systematic name: (2E,6E)-farnesyl-diphosphate diphospho-lyase [cyclising, (–)-drimenol-forming]
Comments: Isolated from the plants Valeriana officinalis (valerian) and Persicaria hydropiper (water pepper). The enzyme does not act on farnesol or drimenol diphosphate. Using 18-oxygen labelled water 18-oxygen was incorporated suggesting involvement of a stabilised carbocation or an equivalent species.
Links to other databases: BRENDA, EXPASY, KEGG, MetaCyc, PDB, CAS registry number:
References:
1. Banthorp, D.V., Brown, J.T. and Morris, G.S. Partial purification of farnesyl pyrophosphate:drimenol cyclase and geranylgerany pyrophosphate:sclareol cyclase, using cell culture as a source of material. Phytochemistry 31 (1992) 3391-3395.
2. Kwon, M., Cochrane, S.A., Vederas, J.C. and Ro, D.K. Molecular cloning and characterization of drimenol synthase from valerian plant (Valeriana officinalis). FEBS Lett. 588 (2014) 4597-4603. [PMID: 25447532]
3. Henquet, M.GL., Prota, N., van der Hooft, J.JJ., Varbanova-Herde, M., Hulzink, R.JM., de Vos, M., Prins, M., de Both, M.TJ., Franssen, M.CR., Bouwmeester, H. and Jongsma, M. Identification of a drimenol synthase and drimenol oxidase from Persicaria hydropiper, involved in the biosynthesis of insect deterrent drimanes. Plant J. 90 (2017) 1052-1063. [PMID: 28258968]
Accepted name: rhizathalene A synthase
Reaction: geranylgeranyl diphosphate = rhizathalene A + diphosphate
For diagram of reaction click here and mechanism click here
Other name(s): TPS08 (gene name)
Systematic name: geranygeranyl-diphosphate diphosphate-lyase (rhizathalene A-forming)
Comments: The enzyme was identified in the roots of the plant Arabidopsis thaliana (thale cress). The product is a semivolatile diterpene that acts as a local antifeedant in belowground direct defense against root-feeding insects.
Links to other databases: BRENDA, EXPASY, KEGG, MetaCyc, CAS registry number:
References:
1. Vaughan, M.M., Wang, Q., Webster, F.X., Kiemle, D., Hong, Y.J., Tantillo, D.J., Coates, R.M., Wray, A.T., Askew, W., O'Donnell, C., Tokuhisa, J.G. and Tholl, D. Formation of the unusual semivolatile diterpene rhizathalene by the Arabidopsis class I terpene synthase TPS08 in the root stele is involved in defense against belowground herbivory. Plant Cell 25 (2013) 1108-1125. [PMID: 23512856]
Accepted name: dolabradiene synthase
Reaction: ent-copalyl diphosphate = dolabradiene + diphosphate
For diagram of reaction click here and mechanism click here.
Glossary: dolabradiene = (4aS,4bR,7S,8aR,10aS)-7-ethenyl-4b,7,10a-trimethyl-1-methylidene-decahydrophenanthrene
Other name(s): KSL4 (gene name)
Systematic name: ent-copalyl-diphosphate diphosphate-lyase (dolabradiene-forming)
Comments: The enzyme, which has been characterized from maize, is involved in the biosynthesis of dolabralexins (type of antifungal phytoalexins).
Links to other databases: BRENDA, EXPASY, KEGG, MetaCyc, CAS registry number:
References:
1. Mafu, S., Ding, Y., Murphy, K.M., Yaacoobi, O., Addison, J.B., Wang, Q., Shen, Z., Briggs, S.P., Bohlmann, J., Castro-Falcon, G., Hughes, C.C., Betsiashvili, M., Huffaker, A., Schmelz, E.A. and Zerbe, P. Discovery, biosynthesis and stress-related accumulation of dolabradiene-derived defenses in maize. Plant Physiol. 176 (2018) 2677-2690. [PMID: 29475898]
Accepted name: eudesmane-5,11-diol synthase
Reaction: (2E,6E)-farnesyl diphosphate + 2 H2O = 7-epi-ent-eudesmane-5,11-diol + diphosphate
For diagram of reaction click here and mechanism click here.
Glossary: 7-epi-ent-eudesmane-5,11-diol = (4S,4aS,6R,8aS)-6-(2-hydroxypropan-2-yl)-4,8a-dimethyldecahydronaphthalen-4a-ol
Other name(s): ZmEDS (gene name)
Systematic name: (2E,6E)-farnesyl-diphosphate diphosphate-lyase (cyclizing, 7-epi-ent-eudesmane-5,11-diol-forming)
Comments: Isolated from the plant Zea mays (maize). The product is named in the reference using a different numbering scheme for eudesmane.
Links to other databases: BRENDA, EXPASY, KEGG, MetaCyc, CAS registry number:
References:
1. Liang, J., Liu, J., Brown, R., Jia, M., Zhou, K., Peters, R.J. and Wang, Q. Direct production of dihydroxylated sesquiterpenoids by a maize terpene synthase. Plant J. 94 (2018) 847-856. [PMID: 29570233]
Accepted name: α-selinene synthase
Reaction: (2E,6E)-farnesyl diphosphate = α-selinene + diphosphate
For diagram of reaction click here
Glossary: α-selinene = (2R,4aR,8aS)-4,8a-dimethyl-2-(prop-1-en-2-yl)-1,2,3,4,4a,5,6,8a-octahydronaphthalene
β-selinene = (4aR,7R,8aS)-4a-methyl-1-methylidene-7-(prop-1-en-2-yl)decahydronaphthalene
aromadendrene = (1aR,4aR,7R,7aR,7bS)-1,1,7-trimethyl-4-methylidenedecahydro-1H-cyclopropa[e]azulene
Other name(s): LfTPS2 (gene name)
Systematic name: (2E,6E)-farnesyl-diphosphate diphosphate-lyase (cyclizing, α-selinene-forming)
Comments: The enzyme from the plant Ocimum basilicum (sweet basil) also produces β-selinene while that from Liquidambar formosana (Formosan sweet gum) also produces traces of aromadendrene.
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. Chuang, L., Wen, C.H., Lee, Y.R., Lin, Y.L., Hsu, L.R., Wang, S.Y. and Chu, F.H. Identification, functional characterization, and seasonal expression patterns of five sesquiterpene synthases in Liquidambar formosana. J Nat Prod 81 (2018) 1162-1172. [PMID: 29746128]
Accepted name: (–)-5-epieremophilene synthase
Reaction: (2E,6E)-farnesyl diphosphate = (–)-5-epieremophilene + diphosphate
For diagram of reaction click here
Glossary: (–)-5-epieremophilene = (3R,4aS,5S)-4a,5-dimethyl-3-(prop-1-en-2-yl)-1,2,3,4,4a,5,6,7-octahydronaphthalene
Other name(s): STPS1 (gene name); STP2 (gene name); STP3 (gene name)
Systematic name: (2E,6E)-farnesyl-diphosphate diphosphate-lyase [cyclizing, (–)-epieremophilene-forming]
Comments: The plant Salvia miltiorrhiza (danshen) produces three different forms of the enzyme, encoded by paralogous genes, that exhibit different spacial expression patterns and respond differently to hormone treatment.
Links to other databases: BRENDA, EXPASY, KEGG, MetaCyc, CAS registry number:
References:
1. Fang, X., Li, C.Y., Yang, Y., Cui, M.Y., Chen, X.Y. and Yang, L. Identification of a novel (-)-5-epieremophilene synthase from Salvia miltiorrhiza via transcriptome mining. Front. Plant Sci. 8 (2017) 627. [PMID: 28487717]
Accepted name: β-pinacene synthase
Reaction: geranylgeranyl diphosphate = β-pinacene + diphosphate
For diagram of reaction click here
Glossary: β-pinacene = 4,8,12-trimethyl-1-(propan-2-yl)cyclotetradeca-1,3,7,11-tetraene
Other name(s): PcS
Systematic name: geranylgeranyl-diphosphate diphosphate-lyase (cyclizing, β-pinacene-forming)
Comments: Isolated from the slime mould Dictyostelium discoideum. The 1-proR hydrogen atom of geranylgeranyl diphosphate is lost in the reaction.
Links to other databases: BRENDA, EXPASY, KEGG, MetaCyc, CAS registry number:
References:
1. Rinkel, J., Rabe, P., Chen, X., Kollner, T.G., Chen, F. and Dickschat, J.S. Mechanisms of the diterpene cyclases β-pinacene synthase from Dictyostelium discoideum and hydropyrene synthase from Streptomyces clavuligerus. Chemistry 23 (2017) 10501-10505. [PMID: 28696553]
Accepted name: hydropyrene synthase
Reaction: geranylgeranyl diphosphate = hydropyrene + diphosphate
For diagram of reaction click here or mechanism click here.
Glossary: hydropyrene = (1R,3aR,3a1S,5aR,5a1S,8aS,10aS)-1,5a,8a-trimethyl-4-methylidenehexadecahydropyrene
Other name(s): HpS
Systematic name: geranylgeranyl-diphosphate diphosphate-lyase (cyclizing, hydropyrene-forming)
Comments: Isolated from the bacterium Streptomyces clavuligerus. The 1-proR hydrogen atom of geranylgeranyl diphosphate is lost in the reaction. The enzyme also produces hydropyrenol, isoelisabethatriene and traces of other diterpenoids. cf. EC 4.2.3.202, hydropyrenol synthase, and EC 4.2.3.203, isoelisabethatriene synthase.
Links to other databases: BRENDA, EXPASY, KEGG, MetaCyc, CAS registry number:
References:
1. Rinkel, J., Rabe, P., Chen, X., Kollner, T.G., Chen, F. and Dickschat, J.S. Mechanisms of the diterpene cyclases β-pinacene synthase from Dictyostelium discoideum and hydropyrene synthase from Streptomyces clavuligerus. Chem. Eur. J. 23 (2017) 10501-10505. [PMID: 28696553]
Accepted name: hydropyrenol synthase
Reaction: geranylgeranyl diphosphate + H2O = hydropyrenol + diphosphate
For diagram of reaction click here or mechanism click here.
Glossary: hydropyrenol = (1R,3aR,3a1R,4S,5aR,5a1S,8aS,10aS)-1,4,5a,8a-tetramethylhexadecahydropyren-4-ol
Other name(s): HpS
Systematic name: geranylgeranyl-diphosphate diphosphate-lyase (cyclizing, hydropyrenol-forming)
Comments: Isolated from the bacterium Streptomyces clavuligerus. The 1-proR hydrogen atom of geranylgeranyl diphosphate is lost in the reaction. The enzyme also produces hydropyrene, isoelisabethatriene and traces of other diterpenoids. cf. EC 4.2.3.201, hydropyrene synthase, and EC 4.2.3.203, isoelisabethatriene synthase.
Links to other databases: BRENDA, EXPASY, KEGG, MetaCyc, CAS registry number:
References:
1. Rinkel, J., Rabe, P., Chen, X., Kollner, T.G., Chen, F. and Dickschat, J.S. Mechanisms of the diterpene cyclases β-pinacene synthase from Dictyostelium discoideum and hydropyrene synthase from Streptomyces clavuligerus. Chem. Eur. J. 23 (2017) 10501-10505. [PMID: 28696553]
Accepted name: isoelisabethatriene synthase
Reaction: geranylgeranyl diphosphate = isoelisabethatriene + diphosphate
For diagram of reaction click here or mechanism click here.
Glossary: isoelisabethatriene = (1S,4R)-4,7-dimethyl-1-[(2R)-6-methylhept-5-en-2-yl]-1,2,3,4,5,6-hexahydronaphthalene
Other name(s): HpS (ambiguous)
Systematic name: geranylgeranyl-diphosphate diphosphate-lyase (cyclizing, isoelisabethatriene-forming)
Comments: Isolated from the bacterium Streptomyces clavuligerus. The 1-proR hydrogen atom of geranylgeranyl diphosphate is involved in a 1,3-hydride shift to the side-chain. The enzyme also produces hydropyrene, hydropyrenol, and traces of other diterpenoids. cf. EC 4.2.3.201, hydropyrene synthase, and EC 4.2.3.202, hydropyrenol synthase.
Links to other databases: BRENDA, EXPASY, KEGG, MetaCyc, CAS registry number:
References:
1. Rinkel, J., Rabe, P., Chen, X., Kollner, T.G., Chen, F. and Dickschat, J.S. Mechanisms of the diterpene cyclases β-pinacene synthase from Dictyostelium discoideum and hydropyrene synthase from Streptomyces clavuligerus. Chem. Eur. J. 23 (2017) 10501-10505. [PMID: 28696553]
Accepted name: valerianol synthase
Reaction: (2E,6E)-farnesyl diphosphate + H2O = valerianol + diphosphate
For diagram of reaction, click here
Glossary: valerianol = 2-[(2R,8R,8aS)-8,8a-dimethyl-1,2,3,4,6,7,8,8a-octahydronaphthalen-2-yl]propan-2-ol
Other name(s): ChTPS1 (gene name); CsiTPS8 (gene name)
Systematic name: (2E,6E)-farnesyl-diphosphate diphosphate-lyase (valerianol-forming)
Comments: The enzyme was characterized from the trees Camellia hiemalis and Camellia sinensis (black tea). The enzyme from Camellia hiemalis produces (2Z,6E)-hedycaryol as a minor product.
Links to other databases: BRENDA, EXPASY, KEGG, MetaCyc, CAS registry number:
References:
1. Hattan, J.I., Shindo, K., Sasaki, T., Ohno, F., Tokuda, H., Ishikawa, K. and Misawa, N. Identification of novel sesquiterpene synthase genes that mediate the biosynthesis of valerianol, which was an unknown ingredient of tea. Sci Rep 8 (2018) 12474. [PMID: 30127518]
Accepted name: sodorifen synthase
Reaction: pre-sodorifen diphosphate = sodorifen + diphosphate
Glossary: pre-sodorifen diphosphate = [(2E)-3-methyl-5-[(1S,4R,5R)-1,2,3,4,5-pentamethylcyclopent-2-en-1-yl]pent-2-en-1-yl phosphonato]oxyphosphonate
sodorifen = (1S,2R,8S)-1,2,4,5,6,7,8-Heptamethyl-3-methylenebicyclo[3.2.1]oct-6-ene
Other name(s): sodD (gene name)
Systematic name: pre-sodorifen diphosphate-lyase [sodorifen-forming]
Comments: The enzyme has been characterized from the bacterium Serratia plymuthica.
Links to other databases: BRENDA, EXPASY, KEGG, MetaCyc, CAS registry number:
References:
1. Domik, D., Magnus, N. and Piechulla, B. Analysis of a new cluster of genes involved in the synthesis of the unique volatile organic compound sodorifen of Serratia plymuthica 4Rx13. FEMS Microbiol. Lett. 363(14) (2016) fnw139. [PMID: 27231241]
2. Schmidt, R., Jager, V., Zuhlke, D., Wolff, C., Bernhardt, J., Cankar, K., Beekwilder, J., Ijcken, W.V., Sleutels, F., Boer, W., Riedel, K. and Garbeva, P. Fungal volatile compounds induce production of the secondary metabolite sodorifen in Serratia plymuthica PRI-2C. Sci Rep 7 (2017) 862. [PMID: 28408760]
3. von Reuss, S., Domik, D., Lemfack, M.C., Magnus, N., Kai, M., Weise, T. and Piechulla, B. Sodorifen biosynthesis in the rhizobacterium Serratia plymuthica involves methylation and cyclization of MEP-derived farnesyl pyrophosphate by a SAM-dependent C-methyltransferase. J. Am. Chem. Soc. 140 (2018) 11855-11862. [PMID: 30133268]
Accepted name: (–)-cyatha-3,12-diene synthase
Reaction: geranylgeranyl diphosphate = (–)-cyatha-3,12-diene + diphosphate
Diagram of reaction click here
Glossary: (–)-cyatha-3,12-diene = (3aS,5aS,10aS)-3a,5a,8-trimethyl-1-(propan-2-yl)-2,3,4,5,6,9,10,10a-octahydrocyclohepta[e]indene
Other name(s): eriG (gene name); CyaTC
Systematic name: geranylgeranyl diphosphate-lyase [(–)-cyatha-3,12-diene-forming]
Comments: The enzyme, characterized from the fungi Hericium erinaceus and Cyathus africanus, requires Mg2+ for activity.
Links to other databases: BRENDA, EXPASY, KEGG, MetaCyc, CAS registry number:
References:
1. Yang, Y.L., Zhang, S., Ma, K., Xu, Y., Tao, Q., Chen, Y., Chen, J., Guo, S., Ren, J., Wang, W., Tao, Y., Yin, W.B. and Liu, H. Discovery and characterization of a new family of diterpene cyclases in bacteria and fungi. Angew. Chem. Int. Ed. Engl. 56 (2017) 4749-4752. [PMID: 28371074]
Accepted name: neoverrucosan-5β-ol synthase
Reaction: geranylgeranyl diphosphate + H2O = neoverrucosan-5β-ol + diphosphate
Diagram of reaction click here
Glossary: neoverrucosan-5β-ol = (1aS,3R,3aS,5aR,8bR,8cS,12S,14S)-1a,3a,5a-trimethyl-8-(propan-2-yl)tetradecahydrocyclopenta[a]cyclopropa[h]naphthalen-3-ol
Other name(s): SapTC1
Systematic name: geranylgeranyl- diphosphate diphosphate-lyase (neoverrucosan-5β-ol-forming)
Comments: Requires Mg2+. Characterized from the marine bacterium Saprospira grandis.
Links to other databases: BRENDA, EXPASY, KEGG, MetaCyc, CAS registry number:
References:
1. Yang, Y.L., Zhang, S., Ma, K., Xu, Y., Tao, Q., Chen, Y., Chen, J., Guo, S., Ren, J., Wang, W., Tao, Y., Yin, W.B. and Liu, H. Discovery and characterization of a new family of diterpene cyclases in bacteria and fungi. Angew. Chem. Int. Ed. Engl. 56 (2017) 4749-4752. [PMID: 28371074]
Accepted name: verrucosan-2β-ol synthase
Reaction: geranylgeranyl diphosphate + H2O = verrucosan-2β-ol + diphosphate
Diagram of reaction click here
Glossary: verrucosan-2β-ol = (1S,3aR,5aS,6aR,7aR,8S,8aR,9bR)-1-(propan-2-yl)tetradecahydrocyclopenta[a]cyclopropa[g]naphthalene-8-ol
Other name(s): ChlTC2
Systematic name: geranylgeranyl-diphosphate diphosphate-lyase (verrucosan-2β-ol-forming)
Comments: Requires Mg2+. Characterized from the bacterium Chloroflexus aurantiacus.
Links to other databases: BRENDA, EXPASY, KEGG, MetaCyc, CAS registry number:
References:
1. Yang, Y.L., Zhang, S., Ma, K., Xu, Y., Tao, Q., Chen, Y., Chen, J., Guo, S., Ren, J., Wang, W., Tao, Y., Yin, W.B. and Liu, H. Discovery and characterization of a new family of diterpene cyclases in bacteria and fungi. Angew. Chem. Int. Ed. Engl. 56 (2017) 4749-4752. [PMID: 28371074]
Accepted name: (R)-axinyssene synthase
Reaction: geranylgeranyl diphosphate = (R)-axinyssene + diphosphate
Diagram of reaction click here
Glossary: (R)-axinyssene = (4R)-4-[(5E)-6,10-dimethylundeca-1,5,9-trien-2-yl]-1-methylcyclohexene
Other name(s): CysTC2
Systematic name: geranylgeranyl-diphosphate diphosphate-lyase [(R)-axinyssene-forming]
Comments: Requires Mg2+. Characterized from the bacterium Archangium violaceum.
Links to other databases: BRENDA, EXPASY, KEGG, MetaCyc, CAS registry number:
References:
1. Yang, Y.L., Zhang, S., Ma, K., Xu, Y., Tao, Q., Chen, Y., Chen, J., Guo, S., Ren, J., Wang, W., Tao, Y., Yin, W.B. and Liu, H. Discovery and characterization of a new family of diterpene cyclases in bacteria and fungi. Angew. Chem. Int. Ed. Engl. 56 (2017) 4749-4752. [PMID: 28371074]
Accepted name: lydicene synthase
Reaction: geranylgeranyl diphosphate = lydicene + diphosphate
Diagram of reaction click here
Glossary: lydicene = (4aR,6aS)-2,2,4α,6α,9-pentamethyl-2,3,4,5,6,7,10,11-octahydro-1Hcyclohepta[a]naphthalene
Other name(s): StlTC
Systematic name: geranylgerany-diphosphate diphosphate-lyase (lydicene-forming)
Comments: Requires Mg2+. Characterized from the bacterium Streptomyces lydicus.
Links to other databases: BRENDA, EXPASY, KEGG, MetaCyc, CAS registry number:
References:
1. Yang, Y.L., Zhang, S., Ma, K., Xu, Y., Tao, Q., Chen, Y., Chen, J., Guo, S., Ren, J., Wang, W., Tao, Y., Yin, W.B. and Liu, H. Discovery and characterization of a new family of diterpene cyclases in bacteria and fungi. Angew. Chem. Int. Ed. Engl. 56 (2017) 4749-4752. [PMID: 28371074]
Accepted name: (+)-exo-β-bergamotene synthase
Reaction: (2E,6E)-farnesyl diphosphate = (+)-exo-β-bergamotene + diphosphate
Diagram of reaction click here and mechanism click here
Glossary: (+)-exo-β-bergamotene = β-trans-bergamotene = (1S,5S,6R)-6-methyl-2-methylidene-6-(4-methylpent-3-enyl)bicyclo[3.1.1]heptane
fumagillin = w(2E,4E,6E,8E)-10-({(3R,4S,5S,6R)-5-methoxy-4-[(2R,3R)-2-methyl-3-(3-methylbut-2-en-1-yl)oxiran-2-yl]-1-oxaspiro[2.5]oct-6-yl}oxy)-10-oxodeca-2,4,6,8-tetraenoate
Systematic name: (2E,6E)-farnesyl-diphosphate diphosphate-lyase [(+)-exo-β-bergamotene-forming]
Comments: The enzyme, characterized from the mold Aspergillus fumigatus, participates in the biosynthesis of the meroterpenoid fumagillin.
Links to other databases: BRENDA, EXPASY, KEGG, MetaCyc, CAS registry number:
References:
1. Lin, H.C., Chooi, Y.H., Dhingra, S., Xu, W., Calvo, A.M. and Tang, Y. The fumagillin biosynthetic gene cluster in Aspergillus fumigatus encodes a cryptic terpene cyclase involved in the formation of β-trans-bergamotene. J. Am. Chem. Soc. 135 (2013) 4616-4619. [PMID: 23488861]
Accepted name: (+)-δ-cadinol synthase
Reaction: (2E,6E)-farnesyl diphosphate + H2O = (+)-δ-cadinol + diphosphate
For diagram of reaction click here
Glossary: (+)-δ-cadinol = (1S,4R,4aS,8aR)-1,6-dimethyl-4-(propan-2-yl)-1,2,3,4,4a,7,8,8a-octahydronaphthalen-1-ol = (+)-torreyol
Other name(s): δ-cadinol synthase (ambiguous)
Systematic name: (2E,6E)-farnesyl-diphosphate diphosphate-lyase [(+)-δ-cadinol-forming]
Comments: The enzyme is involved in the biosynthesis of sesquiterpenoids from (2E,6E)-farnesyl diphosphate in fungi such as Boreostereum vibrans and Coniophora puteana
Links to other databases: BRENDA, EXPASY, KEGG, MetaCyc, CAS registry number:
References:
1. Zhou, H., Yang, Y.L., Zeng, J., Zhang, L., Ding, Z.H. and Zeng, Y. Identification and characterization of a δ-cadinol synthase potentially involved in the formation of boreovibrins in Boreostereum vibrans of basidiomycota. Nat. Prod. Bioprospect. 6 (2016) 167-171. [PMID: 27038475]
2. Ringel, M., Dimos, N., Himpich, S., Haack, M., Huber, C., Eisenreich, W., Schenk, G., Loll, B. and Bruck, T. Biotechnological potential and initial characterization of two novel sesquiterpene synthases from Basidiomycota Coniophora puteana for heterologous production of δ-cadinol. Microb. Cell Fact. 21 (2022) 64. [PMID: 35440053]
Accepted name: colleterpenol synthase
Reaction: all-trans-hexaprenyl diphosphate + H2O = colleterpenol + diphosphate
For diagram of reaction click here
Glossary: colleterpenol = (2S)-2-[(1R,3E,7E,11E)-4,8,12-trimethylcyclotetradeca-3,7,11-trien-1-yl]undeca-5,9-dien-2-ol
Other name(s): CgCS
Systematic name: pentaprenyl-diphosphate diphosphate-lyase [cyclizing, colleterpenol-forming]
Comments: Isolated from Colletotrichum gloeosporioides, a pathogenic fungus that causes bitter rot in variety of crops.
Links to other databases: BRENDA, EXPASY, KEGG, MetaCyc, CAS registry number:
References:
1. Tao, H., Lauterbach, L., Bian, G., Chen, R., Hou, A., Mori, T., Cheng, S., Hu, B., Lu, L., Mu, X., Li, M., Adachi, N., Kawasaki, M., Moriya, T., Senda, T., Wang, X., Deng, Z., Abe, I., Dickschat, J.S. and Liu, T. Discovery of non-squalene triterpenes. Nature 606 (2022) 414-419. [PMID: 35650436]
Accepted name: dolasta-1(15),8-diene synthase
Reaction: geranylgeranyl diphosphate = (5R,12R,14S)-dolasta-1(15),8-diene + diphosphate
For diagram of reaction click here and nechanism click here
Glossary: (5R,12R,14S)-dolasta-1(15),8-diene = (3aR,4aS,8aR)-3a,8a-dimethyl-5-methylene-1-(propan-2-yl)-2,3,3a,4,4a,5,6,7,8,8a,9,10-dodecahydrobenzo[f]azulene
Other name(s): Cg113742 (gene name); CgDS
Systematic name: geranylgeranyl-diphosphate diphosphate-lyase [cyclizing, dolasta-1(15),8-diene-forming]
Comments: Isolated from Colletotrichum gloeosporioides, a pathogenic fungus that causes bitter rot in variety of crops.
Links to other databases: BRENDA, EXPASY, KEGG, MetaCyc, CAS registry number:
References:
1. Bian, G., Rinkel, J., Wang, Z., Lauterbach, L., Hou, A., Yuan, Y., Deng, Z., Liu, T. and Dickschat, J.S. A clade II-D fungal chimeric diterpene synthase from Colletotrichum gloeosporioides produces dolasta-1(15),8-diene. Angew. Chem. Int. Ed. Engl. 57 (2018) 15887-15890. [PMID: 30277637]
Accepted name: δ-araneosene synthase
Reaction: geranylgeranyl diphosphate = δ-araneosene + diphosphate
For diagram of reaction click hereand mechanismclick here
Glossary: δ-araneosene = (3aR,5E,9E)-3a,6,10-trimethyl-1-(propan-2-yl)-2,3,3a,4,7,8,11,12-octahydrocyclopenta[11]annulene
Systematic name: geranylgeranyl-diphosphate diphosphate-lyase [cyclizing, δ-araneosene-forming]
Comments: Isolated from the fungus Colletotrichum gloeosporioidea. δ-Araneosene may be involved in the biosynthesis of dolasta-1(15),8-diene (see EC 4.2.3.214, dolasta-1(15),8-diene synthase) and cycloaraneosene (see EC 4.2.3.191, cycloaraneosene synthase).
Links to other databases: BRENDA, EXPASY, KEGG, MetaCyc, CAS registry number:
References:
1. Bian, G., Rinkel, J., Wang, Z., Lauterbach, L., Hou, A., Yuan, Y., Deng, Z., Liu, T. and Dickschat, J.S. A clade II-D fungal chimeric diterpene synthase from Colletotrichum gloeosporioides produces dolasta-1(15),8-diene. Angew. Chem. Int. Ed. Engl. 57 (2018) 15887-15890. [PMID: 30277637]
Accepted name: somaliensene A synthase
Reaction: geranylfarnesyl diphosphate = somaliensene A + diphosphate
For diagram of reaction click here
Glossary: somaliensene A = (1S,5R,6R)-6-methyl-6-[(3E,7E,11E)-trimethyltrideca-3,7,11-trien-1-yl]bicyclo[3.1.1]hept-2-ene
Other name(s): stsC (gene name)
Systematic name: geranylfarnesyl-diphosphate diphosphate-lyase (cyclizing, somaliensene A-forming)
Comments: A sesterterpenoid synthase enzyme isolated from the bacterium Streptomyces somaliensis. The enzyme also produces somalensene B (cf. EC 4.2.3.217, somaliensene B synthase).
Links to other databases: BRENDA, EXPASY, KEGG, MetaCyc, CAS registry number:
References:
1. Yang, Y., Zhang, Y., Zhang, S., Chen, Q., Ma, K., Bao, L., Tao, Y., Yin, W., Wang, G. and Liu, H. Identification and characterization of a membrane-bound sesterterpene cyclase from Streptomyces somaliensis. J Nat Prod 81 (2018) 1089-1092. [PMID: 29553734]
Accepted name: somaliensene B synthase
Reaction: geranylfarnesyl diphosphate = somaliensene B + diphosphate
For diagram of reaction click here
Glossary: somaliensene B = (4S)-1-methyl-4-[(5E,9E,13E)-6,10,14-trimethylpentadeca-1,5,9,13-tetraen-2-yl]cyclohex-1-ene
Other name(s): stsC (gene name)
Systematic name: geranylfarnesyl-diphosphate diphosphate-lyase (cyclizing, somaliensene B-forming)
Comments: A sesterterpenoid synthase enzyme isolated from the bacterium Streptomyces somaliensis. The enzyme also produces somaliensene A (cf. EC 4.2.3.216, somaliensene A synthase).
Links to other databases: BRENDA, EXPASY, KEGG, MetaCyc, CAS registry number:
References:
1. Yang, Y., Zhang, Y., Zhang, S., Chen, Q., Ma, K., Bao, L., Tao, Y., Yin, W., Wang, G. and Liu, H. Identification and characterization of a membrane-bound sesterterpene cyclase from Streptomyces somaliensis. J Nat Prod 81 (2018) 1089-1092. [PMID: 29553734]
Accepted name: variediene synthase
Reaction: geranylgeranyl diphosphate = variediene + diphosphate
For diagram of reaction click here
Glossary: variediene = (3aR,3bS,6E,10Z,11aR)-3,3,6,10,11a-pentamethyl-2,3,3a,3b,4,5,8,9,11,11a-decahydro-1H-cyclonona[a]pentalene
Other name(s): EvVS
Systematic name: geranylgeranyl-diphosphate diphosphate-lyase (cyclizing, variediene-forming)
Comments: A diterpenoid synthase enzyme isolated from the fungus Aspergillus stellatus.
Links to other databases: BRENDA, EXPASY, KEGG, MetaCyc, CAS registry number:
References:
1. Qin, B., Matsuda, Y., Mori, T., Okada, M., Quan, Z., Mitsuhashi, T., Wakimoto, T. and Abe, I. An unusual chimeric diterpene synthase from Emericella variecolor and its functional conversion into a sesterterpene synthase by domain swapping. Angew. Chem. Int. Ed. Engl. 55 (2016) 1658-1661. [PMID: 26546087]
Accepted name: (2E)-α-cericerene synthase
Reaction: geranylfarnesyl diphosphate = (2E)-α-cericerene + diphosphate
For diagram of reaction click here
Glossary: (2E)-α-cericerene = (1E,4R,7E,11E)-1,7,11-trimethyl-4-[(2E)-6-methylhepta-2,5-dien-2-yl]cyclotetrdeca-1,7,11-triene
Other name(s): EvSS
Systematic name: geranylfarneyl-diphosphate diphosphate-lyase (cyclizing, (2E)-α-cericerene-forming)
Comments: A sesterterpenoid synthase enzyme isolated from the fungus Aspergillus stellatus.
Links to other databases: BRENDA, EXPASY, KEGG, MetaCyc, CAS registry number:
References:
1. Qin, B., Matsuda, Y., Mori, T., Okada, M., Quan, Z., Mitsuhashi, T., Wakimoto, T. and Abe, I. An unusual chimeric diterpene synthase from Emericella variecolor and its functional conversion into a sesterterpene synthase by domain swapping. Angew. Chem. Int. Ed. Engl. 55 (2016) 1658-1661. [PMID: 26546087]
Accepted name: talaropentaene synthase
Reaction: all-trans-hexaprenyl diphosphate = talaropentaene + diphosphate
For diagram of reaction click here
Glossary: talaropentaene = (3aS,5E,9E)-3a,6,10-trimethyl-1-[(2ξ,4E,8E)-undeca-5,9-dien-2-yl]-3,3a,4,7,8,11,12-octahydrocyclopenta[11]annulene
Other name(s): TvTS
Systematic name: pentaprenyl-diphosphate diphosphate-lyase [cyclizing, talaropentaene-forming]
Comments: Isolated from the fungus Talaromyces verruculosus.
Links to other databases: BRENDA, EXPASY, KEGG, MetaCyc, CAS registry number:
References:
1. Tao, H., Lauterbach, L., Bian, G., Chen, R., Hou, A., Mori, T., Cheng, S., Hu, B., Lu, L., Mu, X., Li, M., Adachi, N., Kawasaki, M., Moriya, T., Senda, T., Wang, X., Deng, Z., Abe, I., Dickschat, J.S. and Liu, T. Discovery of non-squalene triterpenes. Nature 606 (2022) 414-419. [PMID: 35650436]
Accepted name: macrophomene synthase
Reaction: all-trans-hexaprenyl diphosphate = macrophomene + diphosphate
For diagram of reaction click here
Glossary: macrophomene = (1S,22R)-tricyclo[20.1.01,22]docosa-2,6,10,14,18-pentaene
Other name(s): MpMS
Systematic name: pentaprenyl-diphosphate diphosphate-lyase [cyclizing, macrophomene-forming]
Comments: Isolated from Macrophomina phaseolina, a pathogenic fungus that causes damping off, seedling blight, collar rot, stem rot, charcoal rot, basal stem rot, and root rot on many plant species. The 22-membered ring in macrophomene represents the largest macrocycle discovered in terpenes so far.
Links to other databases: BRENDA, EXPASY, KEGG, MetaCyc, CAS registry number:
References:
1. Tao, H., Lauterbach, L., Bian, G., Chen, R., Hou, A., Mori, T., Cheng, S., Hu, B., Lu, L., Mu, X., Li, M., Adachi, N., Kawasaki, M., Moriya, T., Senda, T., Wang, X., Deng, Z., Abe, I., Dickschat, J.S. and Liu, T. Discovery of non-squalene triterpenes. Nature 606 (2022) 414-419. [PMID: 35650436]
Accepted name: phomopsene synthase
Reaction: geranylgeranyl diphosphate = phomopsene + diphosphate
For diagram of reaction click here and mechanism click here
Glossary: phomopsene = (1S,6aS,6bR,9aR,10aS)-1,4,7,7,9a-pentamethyl-1,2,3,5,6,6a,6b,7,8,9,9a,10-dodecahydrodicyclopenta[a,d]indene
Other name(s): PaPS; NtPS; NrPS; PmS
Systematic name: geranylgeranyl-diphosphate diphosphate-lyase (cyclizing, phomopsene-formimg)
Comments: A diterpene synthase from the fungus Diaporthe amygdali. Phomopsene synthase has also been isolated from the bacteria Nocardia testacea, Nocardia rhamnosiphila, and Allokutzneria albata. The Allokutzneria albata enzyme also generates allokutznerene (EC 4.2.3.224, allokutznerene synthase), bonnadiene (EC 4.2.3.223, bonnadiene synthase) and traces of (–)-spiroviolene (EC 4.2.3.158, (–)-spiroviolene synthase).
Links to other databases: BRENDA, EXPASY, KEGG, MetaCyc, CAS registry number:
References:
1. Toyomasu, T., Kaneko, A., Tokiwano, T., Kanno, Y., Kanno, Y., Niida, R., Miura, S., Nishioka, T., Ikeda, C., Mitsuhashi, W., Dairi, T., Kawano, T., Oikawa, H., Kato, N. and Sassa, T. Biosynthetic gene-based secondary metabolite screening: a new diterpene, methyl phomopsenonate, from the fungus Phomopsis amygdali. J. Org. Chem. 74 (2009) 1541-1548. [PMID: 19161275]
2. Shinde, S.S., Minami, A., Chen, Z., Tokiwano, T., Toyomasu, T., Kato, N., Sassa, T. and Oikawa, H. Cyclization mechanism of phomopsene synthase: mass spectrometry based analysis of various site-specifically labeled terpenes. J. Antibiot. (Tokyo) 70 (2017) 632-638. [PMID: 28270685]
3. Lauterbach, L., Rinkel, J. and Dickschat, J.S. Two bacterial diterpene synthases from Allokutzneria albata produce bonnadiene, phomopsene, and allokutznerene. Angew. Chem. Int. Ed. Engl. 57 (2018) 8280-8283. [PMID: 29758116]
4. Rinkel, J., Steiner, S.T. and Dickschat, J.S. Diterpene biosynthesis in actinomycetes: studies on cattleyene synthase and phomopsene synthase. Angew. Chem. Int. Ed. Engl. 58 (2019) 9230-9233. [PMID: 31034729]
Accepted name: bonnadiene synthase
Reaction: geranylgeranyl diphosphate = bonnadiene + diphosphate
For diagram of reaction click here and mechanism click here
Glossary: bonnadiene = (1R,7R,7aR,11aR)-1,4,9-trimethyl-7-(propan-2-yl)-2,3,5,6,7,7a,10,11-octahydro-1H-benzo[d]azulene
Other name(s): BdS
Systematic name: geranylgeranyl-diphosphate diphosphate-lyase (cyclizing, bonnadiene-formimg)
Comments: A diterpene synthase isolated from the bacterium Allokutzneria albata. It also generates allokutznerene (EC 4.2.3.224, allokutznerene synthase), phomopsene (EC 4.2.3.222, phomopsene synthase) and traces of (–)-spiroviolene (EC 4.2.3.158, (–)-spiroviolene synthase).
Links to other databases: BRENDA, EXPASY, KEGG, MetaCyc, CAS registry number:
References:
1. Lauterbach, L., Rinkel, J. and Dickschat, J.S. Two bacterial diterpene synthases from Allokutzneria albata produce bonnadiene, phomopsene, and allokutznerene. Angew. Chem. Int. Ed. Engl. 57 (2018) 8280-8283. [PMID: 29758116]
Accepted name: allokutznerene synthase
Reaction: geranylgeranyl diphosphate = allokutznerene + diphosphate
For diagram of reaction click here and mechanism click here
Glossary: allokutznerene = (3S,3aS,7aR,10aR,10bS)-3,6,7a,10,10-pentamethyl-1,2,3,4,5,7,7a,8,9,10,10a,10b-dodecahydrodicyclopenta[d,g]indene
Other name(s): PmS
Systematic name: geranylgeranyl-diphosphate diphosphate-lyase (cyclizing, allokutznerene-formimg)
Comments: A diterpene synthase isolated from the bacterium Allokutzneria albata. It also produces bonnadiene (EC 4.2.3.223, bonnadiene synthase), phomopsene (EC 4.2.3.222, phomopsene synthase) and traces of (–)-spiroviolene (EC 4.2.3.158, (–)-spiroviolene synthase).
Links to other databases: BRENDA, EXPASY, KEGG, MetaCyc, CAS registry number:
References:
1. Lauterbach, L., Rinkel, J. and Dickschat, J.S. Two bacterial diterpene synthases from Allokutzneria albata produce bonnadiene, phomopsene, and allokutznerene. Angew. Chem. Int. Ed. Engl. 57 (2018) 8280-8283. [PMID: 29758116]
Accepted name: cattleyene synthase
Reaction: geranylgeranyl diphosphate = cattleyene + diphosphate
For diagram of reaction click here and mechanism click here
Glossary: cattleyene = (3R,3aS,5aS,5bR,8aR)-3,3a,6,6,8a-pentamethyl-2,3,3a,4,5,5a,5b,6,7,8,8a,9-dodecahydro-1H-pentaleno[2,1-e]indene
Other name(s): CyS
Systematic name: geranylgeranyl-diphosphate diphosphate-lyase (cyclizing, cattleyene-formimg)
Comments: A diterpene synthase isolated from the bacterium Streptantibioticus cattleyicolor.
Links to other databases: BRENDA, EXPASY, KEGG, MetaCyc, CAS registry number:
References:
1. Rinkel, J., Steiner, S.T. and Dickschat, J.S. Diterpene biosynthesis in actinomycetes: studies on cattleyene synthase and phomopsene synthase. Angew. Chem. Int. Ed. Engl. 58 (2019) 9230-9233. [PMID: 31034729]
2. Xing, B., Xu, H., Li, A., Lou, T., Xu, M., Wang, K., Xu, Z., Dickschat, J.S., Yang, D. and Ma, M. Crystal structure based mutagenesis of cattleyene synthase leads to the generation of rearranged polycyclic diterpenes. Angew. Chem. Int. Ed. Engl. 61 (2022) e202209785. [PMID: 35819825]
Accepted name: (+)-2-epi-prezizaene synthase
Reaction: (2Z,6E)-farnesyl diphosphate = (+)-2-epi-prezizaene + diphosphate
Other name(s): EAS3 (gene name); EAS4 (gene name)
Systematic name: (2Z,6E)-farnesyl-diphosphate diphosphate-lyase (cyclizing, (+)-2-epi-prezizaene-forming)
Comments: The enzyme occurs in plants. The initial cyclization product is a (7R)-β-bisabolyl cation. The major final product is (+)-2-epi-prezizaene. Other products are (–)-α-cedrene (cf. EC 4.2.3.227, (–)-α-cedrene synthase), small amounts of (–)-β-curcumene, and other sesquiterpenes with less than 10% yield. The enzyme also catalyses the reaction of EC 4.2.3.61, 5-epiaristolochene synthase.
Links to other databases: BRENDA, EXPASY, KEGG, MetaCyc, CAS registry number:
References:
1. Noel, J.P., Dellas, N., Faraldos, J.A., Zhao, M., Hess, B.A., Jr., Smentek, L., Coates, R.M. and O'Maille, P.E. Structural elucidation of cisoid and transoid cyclization pathways of a sesquiterpene synthase using 2-fluorofarnesyl diphosphates. ACS Chem. Biol. 5 (2010) 377-392. [PMID: 20175559]
2. Faraldos, J.A., O'Maille, P.E., Dellas, N., Noel, J.P. and Coates, R.M. Bisabolyl-derived sesquiterpenes from tobacco 5-epi-aristolochene synthase-catalyzed cyclization of (2Z,6E)-farnesyl diphosphate. J. Am. Chem. Soc. 132 (2010) 4281-4289. [PMID: 20201526]
Accepted name: (–)-α-cedrene synthase
Reaction: (2Z,6E)-farnesyl diphosphate = (–)-α-cedrene + diphosphate
Other name(s): EAS3 (gene name); EAS4 (gene name)
Systematic name: (2Z,6E)-farnesyl-diphosphate diphosphate-lyase (cyclizing, (–)-α-cedrene-forming)
Comments: The enzyme occurs in plants. The initial cyclization product is a (7R)-β-bisabolyl cation. (–)-α-Cedrene is one of the major products. Other products are (+)-2-epi-prezizaene (cf. EC 4.2.3.226, (+)-2-epi-prezizaene synthase), small amounts of (+)-β-curcumene, and other sesquiterpenes with less than 10% yield. The enzyme from Nicotiana tabacum (tobacco) also catalyses the reaction of EC 4.2.3.61, 5-epiaristolochene synthase.
Links to other databases: BRENDA, EXPASY, KEGG, MetaCyc, CAS registry number:
References:
1. Noel, J.P., Dellas, N., Faraldos, J.A., Zhao, M., Hess, B.A., Jr., Smentek, L., Coates, R.M. and O'Maille, P.E. Structural elucidation of cisoid and transoid cyclization pathways of a sesquiterpene synthase using 2-fluorofarnesyl diphosphates. ACS Chem. Biol. 5 (2010) 377-392. [PMID: 20175559]
2. Faraldos, J.A., O'Maille, P.E., Dellas, N., Noel, J.P. and Coates, R.M. Bisabolyl-derived sesquiterpenes from tobacco 5-epi-aristolochene synthase-catalyzed cyclization of (2Z,6E)-farnesyl diphosphate. J. Am. Chem. Soc. 132 (2010) 4281-4289. [PMID: 20201526]
Accepted name: (Z)-β-ocimene synthase
Reaction: geranyl diphosphate = (Z)-β-ocimene + diphosphate
For diagram of reaction click here
Glossary: (Z)-β-ocimene = (3Z)-3,7-dimethyl-1,3,6-octatriene
Other name(s): CsTPS13PK (gene name)
Systematic name: geranyl diphosphate diphosphate lyase [(Z)-β-ocimene-forming]
Comments: The enzyme occurs in flowers (pistillate inflorescences) of Cannabis sativa. The enzyme encoded by CsTPS13PK produces 94% (Z)-β-ocimene from geranyl diphosphate. cf. EC 4.2.3.106, (E)-β-ocimene synthase.
Links to other databases: BRENDA, EXPASY, KEGG, MetaCyc, CAS registry number:
References:
1. Booth, J.K., Page, J.E. and Bohlmann, J. Terpene synthases from Cannabis sativa. PLoS One 12 (2017) e0173911. [PMID: 28355238]
Accepted name: ent-beyerene synthase
Reaction: ent-copalyl diphosphate = ent-beyerene + diphosphate
For diagram of reaction click here and mechanism click here
Glossary: ent-beyerene = ent-beyer-15-ene = beyer-15-ene
Other name(s): ent-kaurene synthase like 2; RcKSL4; OsKSL2; PpCPS/KS (ambiguous)
Systematic name: ent-copalyl-diphosphate diphosphate-lyase (cyclizing, ent-beyerene-forming)
Comments: The enzyme has been shown to occur in castor bean (Ricinus communis) and rice (Oryza sativa). ent-Beyerene is also a product of EC 4.2.3.19 (ent-kaurene synthase) of the moss Physcomitrella patens.
Links to other databases: BRENDA, EXPASY, KEGG, MetaCyc, CAS registry number:
References:
1. Jackson, A.J., Hershey, D.M., Chesnut, T., Xu, M. and Peters, R.J. Biochemical characterization of the castor bean ent-kaurene synthase(-like) family supports quantum chemical view of diterpene cyclization. Phytochemistry 103 (2014) 13-21. [PMID: 24810014]
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