Germacrene

Germacrenes
	(–)-Germacrene A
Names
	IUPAC name (1E,5E,8S)-1,5-dimethyl-8-(prop-1-en-2-yl)cyclodeca-1,5-diene
	Other names (−)-Germacrene A; (E,E)-Germacra-3,9,11-triene; (1E,5E,8S)-1,5-dimethyl-8-(1-methylethenyl)-1,5-cyclodecadiene; (S-(E,E))-1,5-dimethyl-8-(1-methylethenyl)-1,5-cyclodecadiene;
Identifiers
CAS Number	A: 28387-44-2; B: 15423-57-1; C: 34323-15-4; D: 37839-63-7;
3D model (JSmol)	Interactive image; A: Interactive image; B: Interactive image; C: Interactive image; E: Interactive image;
Beilstein Reference	6500908 (A) 1864177 (D)
ChEBI	A: CHEBI:36517; B: CHEBI:5337; C: CHEBI:61478; D: CHEBI:49045;
ChEMBL	B: ChEMBL448125;
ChemSpider	A: 29776407; B: 4444852; D: 28288426;
KEGG	A: C16141; B: C09672; C: C19747;
PubChem CID	A: 9548705; B: 5281519; C: 25244915; D: 5373727; E: 10632030;
	InChI InChI=1S/C15H26/c1-12(2)15-10-8-13(3)6-5-7-14(4)9-11-15/h6,9,12,15H,5,7-8,10-11H2,1-4H3/b13-6+,14-9+/t15-/m0/s1 Key: YDLBHMSVYMFOMI-SDFJSLCBSA-N ; InChI=1/C15H26/c1-12(2)15-10-8-13(3)6-5-7-14(4)9-11-15/h6,9,12,15H,5,7-8,10-11H2,1-4H3/b13-6+,14-9+/t15-/m0/s1 Key: YDLBHMSVYMFOMI-SDFJSLCBBV; A: InChI=1S/C15H24/c1-12(2)15-10-8-13(3)6-5-7-14(4)9-11-15/h6,9,15H,1,5,7-8,10-11H2,2-4H3/b13-6+,14-9+/t15-/m1/s1 Key: XMRKUJJDDKYUHV-DFSVIBJJSA-N; D: InChI=1S/C15H24/c1-12(2)15-10-8-13(3)6-5-7-14(4)9-11-15/h7-8,10,12,15H,3,5-6,9,11H2,1-2,4H3/b10-8-,14-7- Key: GAIBLDCXCZKKJE-BZXLUOIMSA-N; E: InChI=1S/C15H24/c1-12(2)15-10-8-13(3)6-5-7-14(4)9-11-15/h6,9,11,14-15H,1,5,7-8,10H2,2-4H3/b11-9+,13-6+ Key: OAOGSSAAVUPEKA-BMCYRRRCSA-N;
	SMILES C/C/1=C\CC/C(=C/C[C@H](CC1)C(C)C)/C; A: C/C/1=C\CC/C(=C/C[C@@H](CC1)C(=C)C)/C; B: C/C/1=C\CC/C(=C/CC(=C(C)C)CC1)/C; C: C/C/1=C\CC/C(=C/C=C(\CC1)/C(C)C)/C; E: CC\1CC/C=C(/CCC(/C=C1)C(=C)C)\C;
Properties
Chemical formula	C15H24
Molar mass	204.35 g/mol
Density	0.793 g/mL
Boiling point	236.4 °C (457.5 °F; 509.5 K)
	Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa). Infobox references

Germacrenes are a group of naturally occurring volatile organic hydrocarbons of the sesquiterpene and cycloalkene class. They are typically produced in plants and have antimicrobial and insecticidal properties, though they also play a role as insect pheromones. Two prominent molecules are germacrene A and germacrene D.

Structures

Germacrene has five structural isomers.^[1]

*Germacrene isomers*

(–)-Germacrene A	Germacrene B	Germacrene C	Germacrene D	Germacrene E

Germacrene A is chiral and both the (–)-(S) and (+)-(R) forms are found naturally.^[1] Germacrene D is also known in both enantiomeric forms.^[2]

Natural occurrences

The essential oils of deadnettles (genus Lamium),^[3] hedgenettles (genus Stachys),^[4] and Clausena anisata are characterized by their high contents of germacrene D. Germacrene B is a major component of patchouli oil.^[5]

Metabolism in plants

The germacrenes are precursors to sesquiterpene lactones.^[6] For example, the enzyme germacrene A hydroxylase in chicory converts (+)-germacrene A to a carboxylic acid which is the starting material for costunolide synthase, which converts it to costunolide:^[7]^[8]

(+)-germacrene A

Oxidase

(+)-germacrene A acid

Synthase

costunolide

References

1 2 Adio, A. M. (2009). "Germacrenes A–E and related compounds: thermal, photochemical and acid induced transannular cyclizations". Tetrahedron. 65 (8): 1533–1552. doi:10.1016/j.tet.2008.11.050.
↑ Arimura, G.-I.; Huber, D. P. W.; Bohlmann, J. (2004). "Forest tent caterpillars (Malacosoma disstria) induce local and systemic diurnal emissions of terpenoid volatiles in hybrid poplar (Populus trichocarpa × deltoides): cDNA cloning, functional characterization, and patterns of gene expression of (−)-germacrene D synthase, PtdTPS1". The Plant Journal. 37 (4): 603–616. doi:10.1111/j.1365-313X.2003.01987.x. PMID 14756770.
↑ Flamini, G.; Cioni, P. L.; Morelli, I. (2005). "Composition of the essential oils and in vivo emission of volatiles of four Lamium species from Italy: L. purpureum, L. hybridum, L. bifidum and L. amplexicaule". Food Chemistry. 91 (1): 63–68. doi:10.1016/j.foodchem.2004.05.047.
↑ Morteza-Semnani, K.; Akbarzadeh, M.; Changizi, Sh. (2005-11-01). "Essential oils composition of Stachys byzantina, S. inflata, S. lavandulifolia and S. laxa from Iran". Flavour and Fragrance Journal. 21 (2): 300–303. doi:10.1002/ffj.1594.
↑ Hasegawa, Yoshihiro; Tajima, Katsuhiko; Toi, Nao; Sugimura, Yukio (1992). "An additional constituent occurring in the oil from a patchouli cultivar". Flavour and Fragrance Journal. 7 (6): 333–335. doi:10.1002/ffj.2730070608. ISSN 0882-5734.
↑ Ghantous, Akram; Gali-Muhtasib, Hala; Vuorela, Heikki; Saliba, Najat A.; Darwiche, Nadine (2010). "What Made Sesquiterpene Lactones Reach Cancer Clinical Trials?". Drug Discovery Today. 15 (15–16): 668–678. doi:10.1016/0305-1978(86)90101-8. PMID 20541036.
↑ de Kraker JW, Franssen MC, Dalm MC, de Groot A, Bouwmeester HJ (April 2001). "Biosynthesis of germacrene A carboxylic acid in chicory roots. Demonstration of a cytochrome P450 (+)-germacrene a hydroxylase and NADP+-dependent sesquiterpenoid dehydrogenase(s) involved in sesquiterpene lactone biosynthesis". Plant Physiology. 125 (4): 1930–40. doi:10.1104/pp.125.4.1930. PMC 88848. PMID 11299372.
↑ de Kraker JW, Franssen MC, Joerink M, de Groot A, Bouwmeester HJ (May 2002). "Biosynthesis of costunolide, dihydrocostunolide, and leucodin. Demonstration of cytochrome p450-catalyzed formation of the lactone ring present in sesquiterpene lactones of chicory". Plant Physiology. 129 (1): 257–68. doi:10.1104/pp.010957. PMC 155889. PMID 12011356.

Deguerry, F.; Pastore, L.; Wu, S.; Clark, A.; Chappell, J.; Schalk, M. (2006-10-15). "The diverse sesquiterpene profile of patchouli, Pogostemon cablin, is correlated with a limited number of sesquiterpene synthases". Archives of Biochemistry and Biophysics. 454 (2): 123–136. doi:10.1016/j.abb.2006.08.006. PMID 16970904.
Omura, H.; Honda, K.; Feeny, P. (2006-09-01). "From terpenoids to aliphatic acids: further evidence for late-instar switch in osmeterial defense as a characteristic trait of swallowtail butterflies in the tribe Papilionini". Journal of Chemical Ecology. 32 (9): 1999–2012. Bibcode:2006JCEco..32.1999O. doi:10.1007/s10886-006-9124-x. PMID 16902823. S2CID 25242966.
Forcat, S.; Allemann, R. K. (2006-07-07). "Stabilisation of transition states prior to and following eudesmane cation in aristolochene synthase". Organic and Biomolecular Chemistry. 4 (13): 2563–2567. doi:10.1039/b604147g. PMID 16791319.
Bertea, C. M.; Voster, A.; Verstappen, F. W.; Maffei, M.; Beekwilder, J.; Bouwmeester, H. J. (2006-04-15). "Isoprenoid biosynthesis in Artemisia annua: cloning and heterologous expression of a germacrene A synthase from a glandular trichome cDNA library". Archives of Biochemistry and Biophysics. 448 (1–2): 3–12. doi:10.1016/j.abb.2006.02.026. PMID 16579958.
Lou, Y; Baldwin, I. T. (2006-03-01). "Silencing of a germin-like gene in Nicotiana attenuata improves performance of native herbivores". Plant Physiology. 140 (3): 1126–1136. doi:10.1104/pp.105.073700. PMC 1400569. PMID 16461381.
Chang, Y.-J.; Jin, J.; Nam, H.-Y.; Kim, S.-U. (2005-03-01). "Point mutation of (+)-germacrene A synthase from Ixeris dentata". Biotechnology Letters. 27 (5): 285–288. doi:10.1007/s10529-005-0681-9. PMID 15834787. S2CID 21959582.

Germacrene D

Rivero Cruz, B.; Rivero Cruz, I; Rodríguez, J. M.; Cerda García-Rojas, C. M.; Mata, R. (2006-08-01). "Qualitative and quantitative analysis of the active components of the essential oil from 'Brickellia veronicaefolia by nuclear magnetic resonance spectroscopy". Journal of Natural Products. 69 (8): 1172–1176. Bibcode:2006JNAtP..69.1172R. doi:10.1021/np060180b. PMID 16933870.
Yang, F.-Q.; Li, S.-P.; Chen, Y.; Lao, S.-C.; Wang, Y.-T.; Dong, T.-T.; Tsim, K.-W. (2005-09-15). "Identification and quantitation of eleven sesquiterpenes in three species of Curcuma rhizomes by pressurized liquid extraction and gas chromatography-mass spectrometry". Journal of Pharmaceutical and Biomedical Analysis. 39 (3–4): 552–558. doi:10.1016/j.jpba.2005.05.001. PMID 15946818.
Umlauf, D.; Zapp, J.; Becker, H.; Adam, K. P. (2004-09-01). "Biosynthesis of the irregular monoterpene artemisia ketone, the sesquiterpene germacrene D and other isoprenoids in Tanacetum vulgare L. (Asteraceae)". Phytochemistry. 65 (17): 2463–2470. Bibcode:2004PChem..65.2463U. doi:10.1016/j.phytochem.2004.08.019. PMID 15381410.
Agnihotri, V. K.; Thappa, R. K.; Meena, B.; Kapahi, B. K.; Saxena, R. K.; Qazi, G. N.; Agarwal, S. G. (2004-08-01). "Essential oil composition of aerial parts of Angelica glauca growing wild in North-West Himalaya (India)". Phytochemistry. 65 (16): 2411–2413. Bibcode:2004PChem..65.2411A. doi:10.1016/j.phytochem.2004.07.004. PMID 15381015.
Raal, A.; Paaver, U.; Arak, E.; Orav, A. (2004). "Content and composition of the essential oil of Thymus serpyllum L. growing wild in Estonia". Medicina (Kaunas). 40 (8): 795–800. PMID 15300002.
He, X.; Cane, D. E. (2004-03-10). "Mechanism and stereochemistry of the germacradienol/germacrene D synthase of Streptomyces coelicolor A3(2)". Journal of the American Chemical Society. 126 (9): 2678–2679. Bibcode:2004JAChS.126.2678H. doi:10.1021/ja039929k. PMID 14995166.

[Adio-1] 1 2 Adio, A. M. (2009). "Germacrenes A–E and related compounds: thermal, photochemical and acid induced transannular cyclizations". Tetrahedron. 65 (8): 1533–1552. doi:10.1016/j.tet.2008.11.050.

[2] Arimura, G.-I.; Huber, D. P. W.; Bohlmann, J. (2004). "Forest tent caterpillars (Malacosoma disstria) induce local and systemic diurnal emissions of terpenoid volatiles in hybrid poplar (Populus trichocarpa × deltoides): cDNA cloning, functional characterization, and patterns of gene expression of (−)-germacrene D synthase, PtdTPS1". The Plant Journal. 37 (4): 603–616. doi:10.1111/j.1365-313X.2003.01987.x. PMID 14756770.

[3] Flamini, G.; Cioni, P. L.; Morelli, I. (2005). "Composition of the essential oils and in vivo emission of volatiles of four Lamium species from Italy: L. purpureum, L. hybridum, L. bifidum and L. amplexicaule". Food Chemistry. 91 (1): 63–68. doi:10.1016/j.foodchem.2004.05.047.

[4] Morteza-Semnani, K.; Akbarzadeh, M.; Changizi, Sh. (2005-11-01). "Essential oils composition of Stachys byzantina, S. inflata, S. lavandulifolia and S. laxa from Iran". Flavour and Fragrance Journal. 21 (2): 300–303. doi:10.1002/ffj.1594.

[HasegawaTajima1992-5] Hasegawa, Yoshihiro; Tajima, Katsuhiko; Toi, Nao; Sugimura, Yukio (1992). "An additional constituent occurring in the oil from a patchouli cultivar". Flavour and Fragrance Journal. 7 (6): 333–335. doi:10.1002/ffj.2730070608. ISSN 0882-5734.

[6] Ghantous, Akram; Gali-Muhtasib, Hala; Vuorela, Heikki; Saliba, Najat A.; Darwiche, Nadine (2010). "What Made Sesquiterpene Lactones Reach Cancer Clinical Trials?". Drug Discovery Today. 15 (15–16): 668–678. doi:10.1016/0305-1978(86)90101-8. PMID 20541036.

[Franssen-7] Kraker JW, Franssen MC, Dalm MC, de Groot A, Bouwmeester HJ (April 2001). "Biosynthesis of germacrene A carboxylic acid in chicory roots. Demonstration of a cytochrome P450 (+)-germacrene a hydroxylase and NADP+-dependent sesquiterpenoid dehydrogenase(s) involved in sesquiterpene lactone biosynthesis". Plant Physiology. 125 (4): 1930–40. doi:10.1104/pp.125.4.1930. PMC 88848. PMID 11299372.

[8] Kraker JW, Franssen MC, Joerink M, de Groot A, Bouwmeester HJ (May 2002). "Biosynthesis of costunolide, dihydrocostunolide, and leucodin. Demonstration of cytochrome p450-catalyzed formation of the lactone ring present in sesquiterpene lactones of chicory". Plant Physiology. 129 (1): 257–68. doi:10.1104/pp.010957. PMC 155889. PMID 12011356.

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