Disesquiterpene and sesquiterpene coumarins from Ferula pseudalliacea, and determination of their absolute configurations
Graphical abstract
The first disesquiterpene coumarin, a sesquiterpene coumarin, and four known sesquiterpene coumarins were isolated from the roots of Ferula pseudalliacea. The absolute configurations of four of the compounds were established by comparison of experimental and simulated ECD spectra using time dependence density function theory (TDDFT).
Highlights
► Disesquiterpene coumarin and sesquiterpene coumarins were identified in the root extract of Ferula pseudalliacea. ► ECD spectra were used to assign the absolute configurations of compounds. ► Three compounds showed moderate antiplasmodial activity.
Introduction
The genus Ferula (Apiaceae) comprises about 180 species which grow mainly in central Asia, the Middle East, and central Europe (Pimenov and Leonov, 2004). Several species, such as Ferula asafetida, Ferula gumosa and Ferula latisecta have been used in folk medicine to treat stomachache, hysteria, infant colitis, and asthma (Eigner and Scholz, 1999, Zargari, 1997). The genus Ferula is known to be a rich source of biologically active compounds, such as sesquiterpenes (Abd El-Razek et al., 2001, Ahmed, 1999, Iranshahi et al., 2008, Kanani et al., 2011, Tamemoto et al., 2001) and coumarins (Abd El-Razek et al., 2001, Iranshahi et al., 2004, Iranshahi et al., 2007, Iranshahi et al., 2009, Zhou et al., 2000). Ferula pseudalliacea Rech.f. is an indigenous species of the Kurdistan (Sanandaj) mountains in western Iran. As part of a phytochemical study of endemic plants of Iran, and an ongoing screening for new antiprotozoal natural products (Adams et al., 2009a, Adams et al., 2009b, Ślusarczyk et al., 2011), we investigated a n-hexane extract from roots of F. pseudalliacea. We here report on the identification of new disesquiterpene and sesquiterpene coumarins, along with known sesquiterpene coumarins, and on their in vitro antiplasmodial activity. Structures including their absolute configuration were established by a combination of methods, such as 1D and 2D NMR, high-resolution mass spectrometry, single-crystal X-ray analysis, and ECD spectroscopy.
Section snippets
Results and discussion
The n-hexane extract of F. pseudalliacea roots was separated by normal and reversed phase chromatography to give two new (1 and 2) and four known sesquiterpene coumarins (3–6), and a sesquiterpene (Scheme. 1), aristolone (7). Compound 1 was obtained as a colorless gum. Its molecular formula C39H52O5 was deduced from HR-ESIMS (m/z 623.3722 [M+Na]+, calc. 623.3712). The planar structure of 1 was established by analysis of the NMR spectral data. The 13C NMR spectrum displayed 39 carbon signals (
Conclusions
The first disesquiterpene coumarin, a new sesquiterpene coumarin, four known sesquiterpene coumarins, and a sesquiterpene were isolated from the roots of F. pseudalliacea. The configurations of compound 1–4 were determined as 8′S,9′S,10′S,1″S*,9″R*,10″S* (sanandajin), 4′S,5′R,6′S, 8′S,9′S,10′R (kamolonol acetate), 8′S,9′S,10′S, (fekrynol acetate) and 8′S,9′S,10′S, (ethyl galbanate), respectively. The occurrence of sesquiterpene coumarins in higher plants is essentially limited to the families
General experimental procedures
Melting points were determined on an Electrothermal melting point apparatus. Optical rotations were measured on a Perkin-Elmer 341 polarimeter. UV spectra were recorded on a Shimadzu UV-PC 2501 spectrometer. IR spectra were recorded on a Bruker Tensor 27 FT-IR spectrometer. ECD spectra of compounds 1–4 were recorded in MeCN on a AVIV CD spectrometer model 62ADS and analyzed with the AVIV 60DS V4.1 software. NMR spectra were measured on a Bruker DRX-500 spectrometer. HR-ESIMS spectra were
Acknowledgment
We are grateful to Shahid Beheshti University Research Council for partial support of this work.
References (38)
- et al.
Sesquiterpene coumarins from the roots of Ferula assa-foetida
Phytochemistry
(2001) - et al.
Anti-plasmodial flavonoid from Pistacia atlantica
Phytochem. Lett.
(2009) Sesquiterpene coumarins and sesquiterpenes from Ferula sinaica
Phytochemistry
(1999)- et al.
Ferula asa-foetida and Curcuma longa in traditional medical treatment and diet in Nepal
J. Ethnopharmacol.
(1999) - et al.
Sesquiterpene coumarins from Ferula szowitsiana and in vitro antileishmanial activity of 7-prenyloxycoumarins against promastigote
Phytochemistry
(2007) - et al.
Diversolides A–G, guaianolides from the roots of Ferula diversivittata
Phytochemistry
(2008) - et al.
Biologically active alkylated coumarins from Kayea assamica
Phytochemistry
(2003) - et al.
Investigation of some medicinal plants traditionally used for treatment of malaria in Kenya as potential sources of antimalarial drugs
Exp. Parasitol.
(2011) - et al.
A new antiplasmodial coumarin from Toddalia asiatica roots
Fitoterapia
(2000) - et al.
Oxidized aristolane sesquiterpenes from Aristolochia debilis
Phytochemistry
(1984)
Sesquiterpenoids from the fruits of Ferula kuhistanica and antibacterial activity of the constituents of F. kuhistanica
Phytochemistry
Identification of GABA A receptor modulators in Kadsura longipedunculata and assignment of absolute configurations by quantum-chemical ECD calculations
Phytochemistry
Coumarins and bicoumarin from Ferula sumbul: anti-HIV activity and inhibition of cytokine release
Phytochemistry
Protocol for HPLC-based activity profiling for natural products with activities against tropical parasites
Nat. Prod. Commun.
Antimalarial 4-phenylcoumarins from the stem bark of Hintonia latiflora
J. Nat. Prod.
Natural sesquiterpenoids
Nat. Prod. Rep.
Absolute-configurations and circular-dichroism of sesquiterpene-coumarin ethers
Monatsh. Chem.
Cited by (41)
Sesquiterpene coumarins isolated from Ferula bungeana and their anti-neuroinflammatory activities
2022, Bioorganic ChemistryAssessment of therapeutic potential of silver nanoparticles synthesized by Ferula Pseudalliacea rech. F. plant
2022, Inorganic Chemistry CommunicationsCitation Excerpt :In studies with this species, coumarins, sesquiterpenes, esters, sulfur derivatives and monosaccharides, which are biologically active compounds, have been isolated. These compounds have been reported to have biological activities with cytotoxicity, antibacterial, anti-inflammatory, antiviral, anti-cancer and anticoagulant properties [10,11,26,45]. There is no study investigating the synthesis of Ag NPs synthesized from Fp plant extract.
Functionalized nanoclinoptilote as a novel and green catalyst for the synthesis of Mannich bases derived from 4-hydroxy coumarin
2022, Journal of Molecular StructureBioactive sesquiterpene coumarins from the resin of Ferula sinkiangensis targeted on over-activation of microglia
2020, Bioorganic ChemistryCitation Excerpt :The extra precision mode in Glide was applied for docking studies. The chemical profile research of the low polarity fraction of F. sinkiangensis gave nine unreported SCs, ferusingensine A-D (1–4), (8′S, 9′S, 10′S)-propionyl fekrynol (6), ferusingensine F (7), ferusingensine G-H (8–9) and (3′S, 4′S, 5′R, 8′S, 9′S, 10′S)-kamolol acetate (10), one new natural SC, ferusingensine E (5), along with ten known SCs, umbelliprenin (11) [18], fekrynol (12) [19], fekrynol acetate (13) [20], farnesiferone B (14) [21], farnesiferol C (15) [22], farnesiferone A (16) [23], lehmannolone (17) [19], polyanthinin (18) [4], sinkianol A (19) [4], and coladin (20) [24]. The structures of the new SCs were established using HRESIMS, 1D, 2D NMR (1H-1H COSY, HSQC, HMBC and NOESY), [α]D, and ECD spectroscopic techniques.