Planta Med 2006; 72(8): 735-739
DOI: 10.1055/s-2006-931584
Original Paper
Natural Product Chemistry
© Georg Thieme Verlag KG Stuttgart · New York

Calyculatine: a New Dolabellane Diterpenoid from the Marine Sponge Eunicea calyculata

Wei Xiang1 , 2 , Leng Chee Chang1
  • 1Department of Chemistry and Biochemistry, College of Science and Engineering, University of Minnesota Duluth, Duluth, MN, U.S.A.
  • 2Xishuangbanna Tropical Botanical Garden, Chinese Academy of Sciences, Yunnan, P. R. China
Further Information

Publication History

Received: December 23, 2005

Accepted: February 16, 2006

Publication Date:
31 May 2006 (online)

Abstract

A new dolabellane diterpenoid, 7(S)-hydroperoxy-13-keto-(1S,11R)-dolabella-3(E),8(17),12(18)-triene (1), and two known compounds, 7(S),8(S)epoxy-13-keto-1(S),11(R)-dolabella-3(E),12 (18)-diene (2) and 13-keto-1(S),11(R)-dolabella-3(E),7(E),12(18)-triene (3), were isolated from the marine sponge Eunicea calyculata. The structure of 1 was elucidated by 1D 1H- and 13C-NMR spectra and 2D HMQC, HMBC, and the relative stereochemistry was established by analysis of coupling constants and NOESY spectra. In addition, an X-ray crystallographic analysis on a single crystal of 2 was carried out. Compounds 1 and 2 were inactive in the hyphae formation inhibition assay (HFI) in Streptomyces 85E while compound 3 showed inhibitory activity at a concentration of 20 μg/20 μL in the HFI assay.

References

  • 1 Faulkner D J. Marine natural products.  Nat Prod Rep. 1993;  10 497-539
  • 2 Look S A, Fenical W. New bicyclic diterpenoids from the Caribbean gorgonian octocoral Eunicea calyculata .  J Org Chem. 1982;  47 4129-34
  • 3 Shin J, Fenical W. Structures and reactivities of new dolabellane diterpenoids from the Caribbean gorgonian Eunicea laciniata .  J Org Chem. 1991;  56 3392-8
  • 4 Sun H H, Fenical W. Diterpenoids of the brown seaweed Glossophora galapagensis .  Phytochemistry. 1979;  18 340-1
  • 5 Duran R, Zubia E, Ortega M J, Salva J. New diterpenoids from the alga Dictyota dichotoma .  Tetrahedron. 1997;  53 8675-88
  • 6 König G M, Wright A D. New dolabellanes from the marine alga Dictyota pardalis f. pseudohamata .  Tetrahedron. 1994;  50 8011-18
  • 7 De Rosa S, De Stefano S, Macura S, Trivellone E, Zavodnik N. Chemical studies of north adriatic seaweeds-I: new dolabellane diterpenes from the brown alga Dilophus fasciola .  Tetrahedron. 1984;  40 4991-5
  • 8 König G M, Wright A D, Fronczek F R. Extensive 1D and 2D NMR and X-ray studies of diterpenes isolated from the marine alga Dictyota pardalis f. pseudohamata .  J Nat Prod. 1994;  57 1529-38
  • 9 Rodriguez A D, Gonzalez E, Gonzalez C. Additional dolabellane diterpenes from the Caribbean gorgonian octocoral Eunicea laciniata .  J Nat Prod. 1995;  58 226-32
  • 10 Govindan M, Govindan G N, Kingston D JI. Mechanism-based antitumor screening of Caribbean marine organisms: isolation and structure determination of novel diterpenoids from the gorgonian Eunicea tourneforti .  J Nat Prod. 1995;  58 1174-84
  • 11 Gonzalea A G, Martin J D, Norte M, Perez R, Weyler V. A new diterpene from Aplysia dactylomela .  Tetrahedron Lett. 1983;  24 1075-6
  • 12 Hasimoto T, Toyota M, Koyama H, Kikkawa A, Yoshida M, Tanaka M. et al . Novel ent-vibsane- and dolabellane-type diterpenoids from the liverwort Odontoschisma denudatum .  Tetrahedron Lett. 1998;  39 579-82
  • 13 Hunek S, Baxter A, Cameron A F, Connolly J D, Harrison L J, Philips W R. et al .Dolabellane diterpenoids from the liverworts Barbilophozia floerkei, B. lycopodioides, and B. attenuata: spectroscopic and X-ray studies of structure, stereochemistry, and conformation. X-Ray molecular structure of 3S,4S;7S,8S-diepoxy-10R,18-dihydroxydollabellane, 18-acetoxy-3S,4S;7S,8S-diepoxydolabellane, and 10R,18-diacetoxy-3S,4S-epoxydolabell-7E-ene. J Chem Soc Perkin Trans 1 1986: 809-14
  • 14 Mohamed K M, Ohtani K, Kasai R, Yamasaki K. Dolabellane diterpene glucosides from Chrozophora oblique .  Phytochemistry. 1994;  37 495-500
  • 15 Su J, Zhong Y, Shi K, Cheng Q, Snyder K, Hu S. et al . Clavudiol A and clavirolide A, two marine dolabellane diterpenes from the soft coral Clavularia viridis .  J Org Chem. 1991;  56 2337-44
  • 16 Faulkner D J. Marine natural products.  Nat Prod Rep. 2000;  17 7-55
  • 17 Persidis A. Signal transduction as a drug-discovery platform.  Nat Biotechnol. 1998;  16 1082-3
  • 18 Cohen P. Protein kinases, the major drug targets of the twenty-first century.  Nat Rev Drug Discov. 2002;  1 309-15
  • 19 Smith J K, Mamoon N M, Duhe R J. Emerging roles of targeted small molecule protein-tyrosine kinase inhibitors in cancer therapy.  Oncol Res. 2004;  14 175-225
  • 20 Matsumoto A, Hong S K, Ishizuka H, Horinouchi S, Beppu T. Phosphorylation of the AfsR protein involved in secondary metabolism in Streptomyces species by a eukaryotic-type protein kinase.  Gene. 1994;  146 47-56
  • 21 Urabe H, Ogawara H. Cloning, sequencing and expression of serine/threonine kinase-encoding genes from Streptomyces coelicolor A3(2).  Gene. 1995;  153 99-104
  • 22 Vomastek T, Nádvorník R, Janecek J, Techniková Z, Weiser J, Branny P. Characterisation of two putative protein Ser/Thr kinases from actinomycete Streptomyces granaticolor both endowed with different properties.  Eur J Biochem. 1998;  257 55-61
  • 23 Hong S K, Matsumoto A, Horinouchi S, Beppu T. Effects of protein kinase inhibitors on in vitro protein phosphorylation and cellular differentiation of Streptomyces griseus .  Mol Gen Genet. 1993;  236 347-54
  • 24 Waters B, Saxena G, Wanggui Y, Kau D, Wrigley S, Stokes R. et al . Identifying protein kinase inhibitors using an assay based on inhibition of aerial hyphae formation in Streptomyces .  J Antibiot. 2002;  55 407-16
  • 25 Duh C Y, Chia M C, Wang S K, Chen H J, Elgamal A AH, Dai C F. Cytotoxic dolabellane diterpenes from the Formosan soft coral Clavularia inflata .  J Nat Prod. 2001;  64 1028-31
  • 26 Iguchi K, Sawai H, Nishimura H, Fujita M, Yamori T. New dolabellane-type diterpenoids from the Okinawan soft coral of the genus Clavularia .  Bull Chem Soc Jpn. 2002;  75 131-6
  • 27 Umeyama T, Lee P C, Horinouchi S. Protein serine/threonine kinases in signal transduction for secondary metabolism and morphogenesis in Streptomyces .  Appl Microbiol Biotechnol. 2002;  59 419-25
  • 28 Sebolt-Leopold J S, Herrera R. Targeting the mitogen-activated protein kinase cascade to treat cancer.  Nat Rev Cancer. 2004;  4 937-47

Dr. Leng Chee Chang

Department of Chemistry and Biochemistry

246 Chemistry Building

1039 University Drive

University of Minnesota Duluth

Duluth

Minnesota 55812-3020

U.S.A.

Phone: +1-218-726-7346

Fax: +1-218-726-7394

Email: lcchang@d.umn.edu