Sesquiterpene Lactones with Astrodaucane Skeleton from Astrodaucus orientalis

Abstract

Four sesquiterpene lactones, astrodaucanolide A – D (1–4) with unique structures, toghether with two known phenylpropanoid esters (5 and 6) were isolated from a flower extract of Astrodaucus orientalis. The structures were established by 1D and 2D NMR spectroscopy and high-resolution mass spectrometry (HRESIMS), and the absolute configuration of 1–4 was determined by electronic circular dichroism (ECD). Compounds 1–4 novel architecture represents a new class of sesquiterpenes with new skeleton. A putative biosynthetic pathway for their scaffold is proposed with a germacryl cation as the precursor. The suggested biosynthesis pathway is similar to that of eudesmane sesquiterpenes with a different direction of protonation which then leads to the new skeleton, named astrodaucane by the 1,2-methyl migration.

Key words

Astrodaucus orientalis - Apiaceae - sesquiterpene lactone - Astrodaucane - Germacryl cation - Eudesmane

Publication History

Received: 17 October 2021

Accepted after revision: 09 April 2022

Accepted Manuscript online:
09 April 2022

Article published online:
10 January 2023

• References

• 1 Mozaffarian V. The Family of Umbelliferae in Iran: Keys and Distribution. Tehran (Iran): Research Institute of Forest and Rangelands; 1983
• 2 Mozzaffarian V. A Dictionary of Iranian Plant Names. Tehran (Iran): Farhang Moaser Publication; 1998
• 3 Rechinger KH. Flora Iranica, No. 162. Graz (Austria): Akademische Druck and Verlagsanstalt; 1987: 114
• 4 Bazargani YT, Almasirad A, Amin G, Shafiee A. Chemical composition of the essential oils of Astrodaucus persicus (Boiss.) Drude root, stem/leaves and flowers/fruits. Flavour Fragr J 2006; 21: 294-296
• 5 Mazloomifar H, Bigdeli M, Saber-Tehrani M, Rustaiyan A, Masoudi S. Essential Oil of Astrodaucus orientalis (L.) Drude. J Essent Oil Res 2003; 15: 254-255
• 6 Mirza M, Baher Nik Z, Dini M. Chemical composition of the essential oils of Astrodaucus orientalis (L.) Drude leaves and seeds. Flavour Fragr J 2003; 18: 205-206
• 7 Goodarzi S, Hadjiakhoondi A, Yassa N, Khanavi M, Tofighi Z. Essential oils chemical composition, antioxidant activities and total phenols of Astrodaucus persicus . Iran J Basic Med Sci 2016; 19: 159
• 8 Razavi SM, Imanzadeh G, Dolati S, Nejad Ebrahimi S, Majrouhi AA, Zahri S, Ghasemian A. Phytochemical prospection and biological activity of Astrodaucus orientalis (L.) Drude growing wild in Iran. Pharmacologia 2011; 2: 299-303
• 9 Goodarzi S, Nateghpour M, Asgharian P, Hadjiakhoondi A, Yassa N, Tavakoli S, Mirzaei J, Farivar L, Haghi AM, Tofighi Z. Antimalarial and cytotoxic activities of roots and fruits fractions of Astrodaucus persicus (Boiss.) Drude extract. Iran J Basic Med Sci 2017; 20: 1318
• 10 Moradi-Afrapoli F, Shokrzadeh M, Barzegar F, Gorji-Bahri G, Zadali R, Nejad Ebrahimi S. Cytotoxic activity of abietane diterpenoids from roots of Salvia sahendica by HPLC-based activity profiling. Rev Bras Farmacogn 2018; 28: 27-33
• 11 Jassbi AR, Mehrdad M, Eghtesadi F, Nejad Ebrahimi S, Baldwin IT. Novel rearranged abietane diterpenoids from the roots of Salvia sahendica . Chem Biodivers 2006; 3: 916-922
• 12 Hashempour H, Koehbach J, Daly NL, Ghassempour A, Gruber CW. Characterizing circular peptides in mixtures: Sequence fragment assembly of cyclotides from a violet plant by MALDI-TOF/TOF mass spectrometry. Amino Acids 2013; 44: 581-595
• 13 Schmiech L, Uemura D, Hofmann T. Reinvestigation of the bitter compounds in carrots (Daucus carota L.) by using a molecular sensory science approach. J Agric Food Chem 2008; 56: 10252-10260
• 14 Barrero AF, Herrador MM, Arteaga P. Sesquiterpenes and phenylpropanoids from Seseli vayredanum . Phytochemistry 1992; 31: 203-207
• 15 Tabatabaei SM, Nejad Ebrahimi S, Salehi P, Sonboli A, Tabefam M, Kaiser M, Hamburger M, Moridi Farimani M. Antiprotozoal germacranolide sesquiterpene lactones from Tanacetum sonbolii . Planta Med 2019; 85: 424-430
• 16 Frisch MJ, Trucks GWS, Schlegel HB, Scuseria GE, Robb MA, Cheeseman JR, Scalmani G, Barone V, Mennucci B, Petersson GA. Gaussian 09, Revision A02. Wallingford CT: Gaussian, Inc; 2009
• 17 Bruhn T, Schaumlöffel ANU, Hemberger Y, Bringmann G. SpecDis: Quantifying the comparison of calculated and experimental electronic circular dichroism spectra. Chirality 2013; 25: 243-249