Phytochemistry Reviews

, Volume 12, Issue 1, pp 95–105 | Cite as

Cubitane: a rare diterpenoid skeleton

Article

Abstract

There are only 15 diterpenoids known sharing the rare cubitane skeleton (1,3-diisopropyl-6,10-dimethylcyclododecane, Fig. 1) named after the natural product (+)-cubitene ((+)-1) from the termite Cubitermes umbratus. Cubitane-type diterpenoids (“cubitanoids”) have since then been isolated from gorgonian corals and there are reports that cubitene also occurs in plants. The twelve-membered ring of the cubitanoids is an interesting feature for which we have developed a novel synthesis involving bicyclic precursors. In this review, we discuss the state-of-research regarding isolation, structure elucidation, biological activity, biosynthesis, and total synthesis of cubitane-type diterpenoids.
Fig. 1

Cubitane skeleton and cubitanoids from termites

Keywords

Diterpenoids Total synthesis Structure elucidation Cubitane 

References

  1. Araki S, Hatano M, Ito H, Butsugan Y (1987) Samarium(II)-mediated reaction of allylic phosphate esters with carbonyl compounds: a new method for “Umpolung” of allylic phosphates. J Organomet Chem 333:329–335CrossRefGoogle Scholar
  2. Cheng CH, Lin YS, Wen ZH, Su JH (2012) A new cubitane diterpenoid from the soft coral Sinularia crassa. Molecules 17:10072–10078PubMedCrossRefGoogle Scholar
  3. Courtney J, McDonald S (1967) A new C20 α,β-unsaturated aldehyde (3,7,13-trimethyl-10-isopropyl-2,6,11,13-tetradecatetraen-1-al) (I) from tobacco. Tetrahedron Lett 8:459–466CrossRefGoogle Scholar
  4. Friedel M, Golz G, Mayer P, Lindel T (2005) Oxidative cyclization of a seco-cladiellane diterpenoid. Tetrahedron Lett 46:1623–1626CrossRefGoogle Scholar
  5. Gaich T, Baran PS (2010) Aiming for the ideal synthesis. J Org Chem 75:4657–4673PubMedCrossRefGoogle Scholar
  6. Gardner JN, Carlon FE, Gnoj O (1968) One-step procedure for the preparation of tertiary α-ketols from the corresponding ketones. J Org Chem 33:3294–3297PubMedCrossRefGoogle Scholar
  7. Joshi RK, Pande C, Mujawar MHK, Kholkute SD (2009) Chemical composition and antimicrobial activity of the essential oil of Anaphalis nubigena var. monocephala. Nat Prod Commun 4:993–996PubMedGoogle Scholar
  8. Jovanović O, Radulović N, Stojanović G, Palić R, Zlatković B, Gudžić B (2009) Chemical composition of the essential oil of Centaurium erythraea Rafn (Gentianaceae) from Serbia. J Essential Oil Res 21:317–322CrossRefGoogle Scholar
  9. Kodama M, Takahashi T, Kojima T, Itô S (1982) Synthesis of macrocyclic terpenoids by intramolecular cyclization VII. Total synthesis of (±)-cubitene. Tetrahedron Lett 23:3397–3400CrossRefGoogle Scholar
  10. Kodama M, Takahashi T, Kojima T, Ito S (1988) Synthesis of macrocyclic terpenoids by intramolecular cyclization XIII. Stereoselective synthesis of (±)-cubitene, a component of defense secretion of termites. Tetrahedron 44:7055–7062CrossRefGoogle Scholar
  11. Kodama M, Maeda H, Hioki H (1996) Enantioselective synthesis and absolute configuration of (+)-cubitene. Chem Lett 25:809–810Google Scholar
  12. Look SA, Fenical W, Zheng QT, Clardy J (1984) Calyculones, new cubitane diterpenoids from the Caribbean gorgonian octocoral Eunicea calyculata. J Org Chem 49:1417–1423CrossRefGoogle Scholar
  13. Lu M, Lee N, Tseng S, Su J (2011) Sinutriangulin A, a novel diterpenoid from the soft coral Sinularia triangula. Tetrahedron Lett 52:5869–5871CrossRefGoogle Scholar
  14. Marville KI, Reynolds WF, Sealy RL, Tinto WF (2004) Terpenoid metabolites of the marine octocoral Eunicea laciniata. Heterocycles 63:107–113CrossRefGoogle Scholar
  15. McNeil MJ, Porter RBR, Williams LAD, Rainford L (2010) Chemical composition and antimicrobial activity of the essential oils from Cleome spinosa. Nat Prod Commun 5:1301–1306PubMedGoogle Scholar
  16. Nicolaou KC, Denton RM, Lenzen A, Edmonds DJ, Li A, Milburn RR, Harrison ST (2006) Stereocontrolled synthesis of model core systems of lomaiviticins A and B. Angew Chem 118:2130–2135 (Angew Chem Int Ed 45:2076–2081)Google Scholar
  17. Özturk E, Özer H, Çakir A, Mete E, Kandemir A, Polat T (2010) Chemical composition of the essential oil of Tripleurospermum corymbosum E. Hossain, an endemic species from Turkey. J Essent Oil Bearing Plants 13:148–153Google Scholar
  18. Prestwich GD (1984) Interspecific variation of diterpene composition of Cubitermes soldier defense secretions. J Chem Ecol 10:1219–1231CrossRefGoogle Scholar
  19. Prestwich GD, Wiemer DF, Meinwald J, Clardy J (1978) Cubitene: an irregular twelve-membered-ring diterpene from a termite soldier. J Am Chem Soc 100:2560–2561CrossRefGoogle Scholar
  20. Prestwich GD, Jones R, Collins M (1981) Terpene biosynthesis by nasute termite soldiers (Isoptera: Nasutitermitinae). Insect Biochem 11:331–336CrossRefGoogle Scholar
  21. Radetich B, Corey EJ (2002a) A general stereocontrolled, convergent synthesis of oligoprenols that parallels the biosynthetic pathway. J Am Chem Soc 124:2430–2431PubMedCrossRefGoogle Scholar
  22. Radetich B, Corey EJ (2002b) A study of oligoprenyl coupling reactions with allylic stannanes. Org Lett 4:3463–3464PubMedCrossRefGoogle Scholar
  23. Schöttner E, Jones P, Lindel T (2009) Enantiospecific synthesis of a novel rearranged eunicellane diterpenoid by SmI2-mediated cyclization. Synthesis 41(23):3941–3956Google Scholar
  24. Schöttner E, Wiechoczek M, Jones PG, Lindel T (2010) Enantiospecific synthesis of the cubitane skeleton. Org Lett 12:784–787PubMedCrossRefGoogle Scholar
  25. Shin J, Fenical W (1991) New diterpenoids from the Caribbean gorgonian Eunicea calyculata. Photochemical interconversion of the cembrene and cubitene skeletons. J Org Chem 56:1227–1233CrossRefGoogle Scholar
  26. Simon K, Wefer J, Schöttner E, Lindel T (2012) Enantioselective total synthesis of the diterpene (+)-cubitene. Angew Chem 124:11047–11050 (Angew Chem Int Ed 51:10889–10892)CrossRefGoogle Scholar
  27. Springer JP, Clardy J, Cox RH, Cutler HG, Cole RJ (1975) The structure of a new type of plant growth inhibitor extracted from immature tobacco leaves. Tetrahedron Lett 16:2737–2740CrossRefGoogle Scholar
  28. Stojković D, Soković M, Glamočlija J, Džamić A, Ćirić A, Ristić M, Grubišić D (2011) Chemical composition and antimicrobial activity of Vitex agnus-castus L. fruits and leaves essential oils. Food Chem 128:1017–1022CrossRefGoogle Scholar
  29. Su H, Lee N, Lu M, Su J (2012) Triangulene C, a new cubitane-based diterpenoid from the soft coral Sinularia triangula. Nat Prod Commun 7:479–480PubMedGoogle Scholar
  30. Takano S, Kurotaki A, Takahashi M, Ogasawara K (1987) Chiral route to cis-caronaldehyde from d-mannitol. J Chem Soc Perkin Trans 1:91–97CrossRefGoogle Scholar
  31. Tempesta MS, Pawlak JK, Iwashita T, Naya Y, Nakanishi K, Prestwich GD (1984) Cubugene, a diterpenoid with a novel carbon skeleton from a termite soldier (Isoptera Termitidae Termitinae). J Org Chem 49:2077–2079CrossRefGoogle Scholar
  32. Umbreit MA, Sharpless KB (1977) Allylic oxidation of olefins by catalytic and stoichiometric selenium dioxide with tert-butyl hydroperoxide. J Am Chem Soc 99:5526–5528CrossRefGoogle Scholar
  33. Vig OP, Bari SS, Trehan IR, Vig R (1980) Synthesis of (±)-cubitene, a twelve-membered monocyclic diterpene isolated from the termite Cubitermes umbratus Williams. Indian J Chem, Sect B: Org Chem Incl Med Chem 19B:446–449Google Scholar
  34. Wahlberg I, Eklund AM (1992) Cembranoids, pseudoterpanoids, and cubitanoids of natural occurrence. In: Zechmeister L, Herz W, Grisebach H, Kirby GW (eds) Progress in the chemistry of organic natural products, vol 59. Springer, Vienna, pp 141–294Google Scholar
  35. Wei X, Nieves K, Rodríguez AD (2012) Bioactive cubitane diterpenoids from a Colombian gorgonian species of the genus Eunicea. Pure Appl Chem 84:1847–1855CrossRefGoogle Scholar
  36. Wiemer DF, Meinwald J, Prestwich GD, Miura I (1979) Cembrene A and (3Z)-cembrene A: diterpenes from a termite soldier (Isoptera Termitidae Termitinae). J Org Chem 44:3950–3952CrossRefGoogle Scholar
  37. Wiemer DF, Meinwald J, Prestwich GD, Solheim BA, Clardy J (1980) Biflora-4,10(19),15-triene: a new diterpene from a termite soldier (Isoptera Termitidae Termitinae). J Org Chem 45:191–192CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media Dordrecht 2012

Authors and Affiliations

  1. 1.Institute of Organic ChemistryTechnische Universität BraunschweigBraunschweigGermany

Personalised recommendations