Chemical and Genetic Identity of Ligularia tsangchanensis and L. muliensis . Isolation of a Cacalol Precursor from a Hybrid of L. tsangchanensis and L. vellerea
Free accessResearch articleFirst published online April, 2018
Chemical and Genetic Identity of Ligularia tsangchanensis and L. muliensis . Isolation of a Cacalol Precursor from a Hybrid of L. tsangchanensis and L. vellerea
The chemical composition and the DNA sequence of an evolutionarily neutral region were studied for three samples of L. tsangchanensis, three samples of L. muliensis, and one sample of a hybrid between L. tsangchanensis and L. vellerea. L. tsangchanensis and L. muliensis were indistinguishable in the chemical composition and the ITS sequence, supporting a recent taxonomic study that merged the two species into L. tsangchanensis. Cacalol (1) was isolated as the most major component from both L. tsangchanensis and L. muliensis, while 6-acetoxy-9-oxofuranoeremophilane (10), a putative cacalol precursor, was isolated from the hybrid.
LiuS.W., DengD.S., LiuJ.Q. (1994) The origin, evolution and distribution of Ligularia Cass. (Compositae). Acta Phytotaxonomica Sinica, 32, 514–524.
2.
KurodaC., HanaiR., NaganoH., ToriM., GongX. (2012) Diversity of furanoeremophilanes in major Ligularia species in the Hengduan Mountains. Natural Product Communications, 7, 539–548.
3.
KurodaC., HanaiR., ToriM., OkamotoY., SaitoY., NaganoH., OhsakiA., HirotaH., KawaharaT., GongX. (2014) Diversity in furanoeremophilane composition produced by Ligularia species (Asteraceae) in the Hengduan Mountains area of China. Journal of Synthetic Organic Chemistry Japan, 72, 717–725.
4.
ToriM., HondaK., NakamizoH., OkamotoY., SakaokuM., TakaokaS., GongX., ShenY., KurodaC., HanaiR. (2006) Chemical constituents of Ligularia virgaurea and its diversity in southwestern Sichuan of China. Tetrahedron, 62, 4988–4995.
5.
NaganoH., IwazakiY., GongX., ShenY., KurodaC., HanaiR. (2006) Chemical and genetic differentiation of Ligularia pleurocaulis in northwestern Yunnan and southwestern Sichuan Provinces of China. Bulletin of the Chemical Society of Japan, 79, 300–304.
6.
HanaiR., GongX., ToriM., KondoS., OtoseK., OkamotoY., NishihamaT., MurotaA., ShenY., WuS., KurodaC. (2005) Chemical and genetic study of Ligularia tongolensis, Ligularia cymbulifera, and Ligularia atroviolacea in the Hengduan Mountains of China. Bulletin of the Chemical Society of Japan, 78, 1302–1308.
7.
LiuS., IllarionovaI.D. (2011) Ligularia. In Flora of China, Vol. 20–21, WuZ.Y., RavenP.H., HongD.Y. (Eds). Science Press (Beijing) and Missouri Botanical Garden Press (St. Louis), 376–415.
8.
IllarionovaI., WangL., YangQ.E. (2017) Ligularia muliensis (Asteraceae, Senecioneae) is merged with L. tsangchanensis. Phytotaxa, 299, 169–184.
9.
TorihataA., HanaiR., GongX., ShenY., KurodaC. (2007) Chemical and genetic differentiation of Ligularia tsangchanensis in Yunnan and Sichuan Provinces of China. Chemistry and Biodiversity, 4, 500–507.
10.
TerabeM., TadaM., TakahashiT. (1978) Absolute stereochemistry of cacalol. Bulletin of the Chemical Society of Japan, 51, 661–662.
11.
GaikwadN.G., MadyasthaK.M. (2002) Biosynthesis of β-substituted furan skeleton in the lower furanosesquiterpenoids: a model study. Biochemical and Biophysical Research Communications, 290, 589–594.
12.
WuQ.H., LiuC.M., ChenY.J., GaoK. (2006) Terpenoids from the roots of Ligularia muliensis. Helvetica Chimica Acta, 89, 915–922.
13.
ToriM., NakamizoH., MiharaK., SatoM., OkamotoY., NakashimaK., TanakaM., SaitoY., SonoM., GongX., ShenY., HanaiR., KurodaC. (2008) Chemical and genetic diversity of Ligularia vellerea in Yunnan, China. Phytochemistry, 69, 1158–1165.
14.
(a) KurodaC., UeshinoT., NaganoH. (2004) Ehrlich's reaction of furanoeremophilanes. Bulletin of the Chemical Society of Japan, 77, 1737–1740; (b) Kuroda C, Nishio E. (2007) Substituent effect in color of Ehrlich's test of tetrahydrobenzofuran. Natural Product Communications, 2, 581–585.
15.
RomoJ., Joseph-NathanP. (1964) The constituents of Cacalia decomposita A. Gray. Structures of cacalol and cacalone. Tetrahedron, 20, 2331–2337.
16.
NayaK., MiyoshiY., MoriH., TakaiK., NakanishiM. (1976) The sesquiterpenes of Cacalia species. Chemistry Letters, 73–76.
17.
SaitoY., TakashimaY., KamadaA., SuzukiY., SuenagaM., OkamotoY., MatsunagaY., HanaiR., KawaharaT., GongX., ToriM., KurodaC. (2012) Chemical and genetic diversity of Ligularia virgaurea collected in northern Sichuan and adjacent areas of China. Isolation of 13 new compound. Tetrahedron, 68, 10011–10029 (Corrigendum: Tetrahedron, 70, 1099).
18.
YusteF., DíazE., WallsF., JankowskiK. (1976) The structure of cacalone. The Journal of Organic Chemistry, 41, 4103–4106.
19.
OmuraK., NakanishiM., TakaiK., NayaK. (1978) The sesquiterpenes of Cacalia species: 8-oxocacalol and the stereochemistry of cacalone epimers. Chemistry Letters, 1257–1260.
20.
NayaK., TakaiK., NakanishiM., OmuraK. (1977) The Sesquiterpenes of Cacalia species. II. The structure of cacalal and the interconversions of the constituent. Chemistry Letters, 1179–1182.
21.
KuroyanagiM., NaitoH., NoroT., UenoA., FukushimaS. (1985) Furanoeremophilane-type sesquiterpenes from Cacalia adenostyloides. Chemical and Pharmaceutical Bulletin, 33, 4792–4797.
22.
JiaZ., ChenH. (1991) Benzofuranosesquiterpenes from Ligularia virgaurea. Phytochemistry, 30, 3132–3134.
23.
(a) Rodriguez-HahnL., GuzmanA., RomoJ. (1968) The constituents of Cacalia decomposita. IV. Structure of decompostin. Tetrahedron, 24, 477–483; (b) Samek Z, Harmatha J, Novotný L, Šorm F. (1969) Terpenes. CCII. Absolute configuration of adenostylone, neoadenostylone, and isoadenostylone from Adenostyles alliariae (Gouan) Kern, and of decompostin from Cacalia decomposita A. Gray. Collection of Czechoslovak Chemical Communications, 34, 2792–808.
24.
NaganoH., KurodaC., MoriyamaY., TsuyukiT., TakahashiT. (1982) Mass spectra of furanoeremophilane derivatives. Bulletin of the Chemical Society of Japan, 55, 1221–1227.
25.
(a) IshiiH., TojioT., MinatoH. (1965) Sesquiterpenoids. IX. Structure of ligularol and ligularone from Ligularia sibirica. Tetrahedron, 21, 2605–2610. (b) Bohlmann F, Zdero C, Mahanta PK. (1977) Neue eremophilan-derivate aus Lopholaena-arten. Phytochemistry, 16, 1769–1771.
26.
KřepinskýJ., MotlO., DolejšL., NovotnýL., HeroutV., BatesR.B. (1968) Terpenes. CXCIV. The structure of eremophilene, the sesquiterpenic hydrocarbon from Petasites genus. Tetrahedron Letters, 29, 3315–3318.
27.
GuerrieroA., PietraF. (1982) Furanoeremophilanes from Petasites niveus: High solvolytic reactivity at the C-6β Position bearing an α,β-unsaturated ester group. Phytochemistry, 21, 2887–2891.
28.
KurodaC., ShibayamaC., InoueK., OkamotoY., ToriM., SaitoY., HanaiR., GongX. (2016) Chemical Lineages of Ligularia fischeri. Natural Product Communications, 11, 139–143.
29.
BohlmannF., JakupovicJ., WarningU., GrenzM., Chau-ThiT.V., KingR.M., RobinsonH. (1986) Sesquiterpenes with new carbon skeletons, furoeremophilanes, secoeremophilanes and other constituents from Argentinian Senecio species. Bulletin des Sociétés Chimiques Belges, 95, 707–736.
30.
JakupovicJ., PathakV.P., GrenzM., BenerjeeS., WolfrumC., BaruahR.N., BohlmannF. (1987) Sesquiterpene derivatives from Othonna and related species. Phytochemistry, 26, 1049–1052.
31.
(a) SaitoY., IchiharaM., TakashimaY., OkamotoY., GongX., HanaiR., KurodaC., ToriM. (2017) Chemical constituents of hybrids of Ligularia cyathiceps and L lamarum/L. subspicata collected in China: Structures of subspicatins M, N, O1, and O2, and related compounds. Phytochemistry, 140, 69–76; (b) Shimizu A, Watanabe S, Hanai R, Okamoto Y, Tori M, Gong X, Kuroda C. (2014) Chemical and genetic study on hybrid of Ligularia subspicata and L. cyathiceps collected in Yunnan Province of China. Chemistry and Biodiversity, 11, 1438–1448.
32.
NaganoH., TorihataA., MatsushimaM., HanaiR., SaitoY., BabaM., TanioY., OkamotoY., TakashimaY., IchiharaM., GongX., KurodaC., ToriM. (2009) Chemical and genetic study of Ligularia cyathiceps in Yunnan Province of China. Helvetica Chimica Acta, 92, 2071–2081.
33.
NaganoH., MatsushimaM., YamadaH., HanaiR., GongX., KurodaC. (2010) Two new furanoeremophilane sesquiterpenoids from Ligularia oligonema. Natural Product Communications, 5, 1–4.
