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Planta Med 2005; 71(12): 1140-1144
DOI: 10.1055/s-2005-873132
Original Paper
Natural Product Chemistry
© Georg Thieme Verlag KG Stuttgart · New York

New Eremophilenolides from Cacalia pilgeriana

Er-Wei Li1 , Jing Pan2 , Kun Gao1 , Zhong-Jian Jia1
  • 1State Key Laboratory of Applied Organic Chemistry, College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou, P. R. China
  • 2School of Life Sciences, Lanzhou University, Lanzhou, P. R. China
Further Information

Publication History

Received: March 20, 2005

Accepted: May 27, 2005

Publication Date:
14 October 2005 (online)

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Abstract

Five new eremophilenolides and a known sesquiterpene were isolated from the methanol extract of the roots of Cacalia pilgeriana. Their structures were identified as 1β-hydroxy-2β-methyl-senecioyloxyeremophil-7(11)-en-8β(12)-olide (1), 1β-hydroxy-2β-methylsenecioyloxy-8α-methoxyeremophil-7(11)-en- 8β(12)-olide (2), 2β-hydroxy-3β-methylsenecioyloxyeremophil-7(11)-en-8α(12)-olide (3), 2β,8β-dihydroxy-3β-methylsenecioyloxyeremophil-7(11)-en-8α(12)-olide (4) and 1β,8β-dihydroxy-2β,3α-diangeloyloxyeremophil-7(11)-en-8α(12)-olide (5) and caryolane-1,9β-diol (6) by spectroscopic methods including 2D-NMR techniques (1H-1H COSY, HMQC, HMBC) and HR-ESI-MS. The structure and relative stereochemistry of compound 1 were unequivocally established by X-ray diffraction analysis. Bioassays showed compounds 3 and 5 to possess strong cytotoxic activity in vitro against human leukemia cells (HL-60) (IC50 < 15 μg mL-1). The structure-activity relationship is discussed.

Key words

Cacalia pilgeriana - Compositae - eremophilenolides - sesquiterpenes - cytotoxic activity

References

  • 1 How K C. A Dictionary of the Families and Genera of Chinese Seed Plants. 2nd edn. Beijing; Science Press 1998: p 75
    Search in Google Scholar
  • 2 Chinese Crude Drugs C o. Zhongguo Zhongyao Ziyuan Zhiyao. Beijing; Science Press 1994: p 1271
    Search in Google Scholar
  • 3 Xue Z W, Yu Y Q. Index Flora of Chinese Medicinal Herbs. Beijing; People’s Health Press 1996: p 754
    Search in Google Scholar
  • 4 Correa J, Romo J. The constituents of Cacalia decomposita. A. Gray: structures of maturin, maturinin, maturone and maturinone. Tetrahedron 1966: 685-91
    Search in Google Scholar
  • 5 Joseph-Nathan P, Negreta M C, Gonzalez M P. Studies in Cacalia species.  Phytochemistry. 1970;  9 1623-8
    CrossrefPubMedSearch in Google Scholar
  • 6 Takemoto T, Kusano G, Aota K, Kaneshima M, Emary N A. Studies on the constituents of Cacalia spp. I. The constituents of Cacalia auriculata DC. var. kamtschatica (Maxim.) Matsumura. (1).  Yakugaku Zasshi. 1974;  94 1593-6
    PubMedSearch in Google Scholar
  • 7 Naya K, Miyoshi Y, Mori H, Takai K, Nakanishi M. The sesquiterpenes of Cacalia species. Chem Lett 1976: 73-6
    Search in Google Scholar
  • 8 Casares A, Maldonado L A. The structure of cacalone. Tetrahedron Lett 1976: 2485-8
    Search in Google Scholar
  • 9 Naya K, Takai K, Nakanishi M, Omura K. The sesquiterpenes of Cacalia species II. The structure of cacalal and the interconversions of the constituents. Chem Lett 1977: 1179-82
    Search in Google Scholar
  • 10 Omura K, Nakanishi M, Takai K, Naya K. The sesquiterpenes of Cacalia species: 8-oxocacalol and the stereochemistry of cacalone epimers. Chem Lett 1978: 1257-60
    Search in Google Scholar
  • 11 El-Emary N A, Takemoto T, Kusano G. New sesquiterpenes from the roots of Cacalia auriculata .  Planta Med. 1980;  38 161-4
    PubMedSearch in Google Scholar
  • 12 Kuroyanagi M, Naito H, Noro T, Ueno A, Fukushima S. Furanoeremophilane-type sesquiterpenes from Cacalia adenostyloides .  Chem Pharm Bull. 1985;  33 4792-7
    PubMedSearch in Google Scholar
  • 13 Krasovskaya N P, Kulesh N I, Denisenko V A. Natural antioxidants furanoeremophilanes from Cacalia root.  Khim Prir Soedin. 1989;  5 643-5
    PubMedSearch in Google Scholar
  • 14 Rodriguez-Hahn L, Guzman A, Romo J. Constituents of Cacalia decomposita. IV. Structure of decompostin. Tetrahedron 1968: 477-83
    Search in Google Scholar
  • 15 Samek Z, Harmatha J, Novotny L, Sorm F. Absolute configuration of adenostylone, neoadenostylone and isoadenostylone from Adenostyles alliariae (Gouan) Kern, and decompostin from Cacalia decomposita A. Gray.  Coll Czech Chem Commun. 1969;  34 2792-807
    PubMedSearch in Google Scholar
  • 16 Hayashi K, Nakamura H, Mitsuhashi H. Sesequiterpenes from Cacalia hastate .  Phytochemistry. 1973;  12 2931-3
    CrossrefPubMedSearch in Google Scholar
  • 17 Zhang S M, Zhao G L, Li R, Lin G Q. Eremophilane sesquiterpenes from Cacalia roborowskii .  Phytochemistry. 1998;  48 519-24
    CrossrefPubMedSearch in Google Scholar
  • 18 Mao M J, Jia Z J. Eremophilane sesquiterpenes from Cacalia ainsliaeflora .  Planta Med. 2001;  67 1-5
    PubMedSearch in Google Scholar
  • 19 Mao M J, Yang Z D, Jia Z J. New eremophilane sesquiterpenes from Cacalia ainsliaeflora .  Planta Med. 2003;  69 745-9
    Thieme ConnectPubMedSearch in Google Scholar
  • 20 Wang Y, Yang M, Yuan C S, Han Y F, Jia Z J. Sesquiterpenes and other constituent from Cacalia deltophylla .  Pharmazie. 2003;  58 596-8
    PubMedSearch in Google Scholar
  • 21 Wang P F, Yang C, Jia Z J. Studies on the chemical constituents of Cacalia pilgeriana .  J Lanzhou Univ (Natural Sciences). 2003;  39 61-3
    PubMedSearch in Google Scholar
  • 22 Shao H J, Feng J T, Han J, Li G Z, Zhang X. Primary study on antifugal activity of 32 plant extracts.  J Northwest Sci Tech Univ Agric For. 2003;  31 59-62
    PubMedSearch in Google Scholar
  • 23 Skehan P, Storeng R, Scudiero D. New colorimetric cytotoxicity assay for anticancer-drug screening.  J Natl Cancer Inst. 1990;  82 1107-12
    CrossrefPubMedSearch in Google Scholar
  • 24 Heymann H, Tezuka Y, Kikuchi T, Supriyatna S. Constituents of Sindora sumatrana Miq. I. Isolation and NMR spectral analysis of sesquiterpenes from the dried pods.  Chem Pharm Bull. 1994;  42 138-46
    PubMedSearch in Google Scholar
  • 25 Ying B P, Yang P M, Zhu H R. Studies on the chemical constituents of Tussilago farfara L. I. The structure of farfaratone.  Acta Chim Sin. 1987;  45 450-5
    PubMedSearch in Google Scholar
  • 26 Wang C D, Gao L JN, Mi C F, Qiao B L, Yang J, Zheng Q T. et al . Studies on the chemical constituents of Tussilago farfara L.  Acta Pharm Sin. 1989;  24 913-6
    PubMedSearch in Google Scholar
  • 27 Wang W S, Gao K, Jia Z J. New eremophilenolides from Ligulariopsis shichuana .  J Nat Prod. 2002;  65 714-7
    CrossrefPubMedSearch in Google Scholar
  • 28 Li X Q, Gao K, Jia Z J. Eremophilenolides and other constituent from the roots of Ligularia sagitta .  Planta Med. 2003;  69 356-60
    Thieme ConnectPubMedSearch in Google Scholar
  • 29 Zhao Y, Parsons S, Smart B A, Tan R X, Jia Z J, Sun H D, Rankin D WH. Eremophilane derivatives with a novel carbon skeleton from Ligularia veitchiana .  Tetrahedron. 1997;  53 6195-208
    CrossrefPubMedSearch in Google Scholar
  • 30 Yaoita Y, Kikuchi M. Structures of new eremophilane derivatives from the rhizomes of Petasites japonicus Maxim.  Chem Pharm Bull. 1995;  43 1738-43
    PubMedSearch in Google Scholar
  • 31 Naya K, Kanazawa R, Sawada M. The photosensitized oxygenation of furanoeremophilanes I. The isomeric hydroperoxides from petasalbin and their transformations to lactones.  Bull Chem Soc Jpn. 1975;  48 3220-5
    PubMedSearch in Google Scholar
  • 32 Naya K, Nogi N, Makiyama Y, Takashina H, Imagawa T. The photosensitized oxygenation of furanoeremophilanes II. The Preparation and stereochemistry of the isomeric hydroperoxides and the corresponding lactones from furnaofukinin and furanoeremophilanes.  Bull Chem Soc Jpn. 1977;  50 3002-6
    PubMedSearch in Google Scholar
  • 33 Sugama K, Hayashi K, Mitsuhashi H. Eremophilenolides from Petasites japonicus .  Phytochemistry. 1985;  24 1531-5
    CrossrefPubMedSearch in Google Scholar
  • 34 Lin Y L, Ou J C, Chrn C F, Kuo Y H. Eremophilanes from Petasites formosanus Kitamura.  Chem Pharm Bull. 1998;  46 1807-9
    PubMedSearch in Google Scholar

Prof. Zhong-Jian Jia

College of Chemistry and Chemical Engineering

State Key Laboratory of Applied Organic Chemistry

Lanzhou University

Lanzhou 730000

People’s Republic of China

Fax: +86-0931-891-2582

Email: jiazj@lzu.edu.cn

Email: miaozm@lzu.edu.cn