The marine sponge Haliclona fulva (previously described as Reniera fulva) is widespread in the Mediterranean Sea. The chemical study of the sponge led to the isolation and identification of a new compound: 3-epi-cladocroic acid (1) alongside the previously reported cladocroic acid (2) and some other known compounds previously isolated. The structure was fully determined on the basis of extensive analysis by 1D and 2D NMR, as well as GC-MS/MS. The absolute configuration was determined by comparison of the experimental electronic circular dichroism (ECD) spectra with theoretically calculated spectra; these results may be extended to other asymetric cyclopropane carboxylic acids.
References
[1]
Van Soest, R.; Boury-Esnault, N.; Hooper, J.; Rützler, K.; de Voogd, N.; Alvarez de Glasby, B.; Hajdu, E.; Pisera, A.; Manconi, R.; Schoenberg, C.; et al. World Porifera Database. 2011. Available online: http://www.marinespecies.org/ (accessed on 16 December 2012).
[2]
Cimino, G.; de Stefano, S. New acetylenic compounds from the sponge Reniera fulva. Tetrahedron Lett. 1977, 18, 1325–1328, doi:10.1016/S0040-4039(01)93008-4.
[3]
Ortega, M.J.; Zubía, E.; Carballo, J.L.; Salvá, J. Fulvinol, a new long-chain diacetylenic metabolite from the sponge Reniera fulva. J. Nat. Prod. 1996, 59, 1069–1071, doi:10.1021/np960436l.
[4]
Zubía, E.; Ortega, M.J.; Carballo, J.L.; Salvá, J. Sesquiterpene hydroquinones from the sponge Reniera mucosa. Tetrahedron 1994, 50, 8153–8160.
[5]
Defant, A.; Mancini, I.; Raspor, L.; Guella, G.; Turk, T.; Sep？i？, K. New structural insights into saraines A, B, and C, macrocyclic alkaloids from the mediterranean sponge Reniera (Haliclona) sarai. Eur. J. Org. Chem. 2011, 2011, 3761–3767.
[6]
Jang, K.H.; Kang, G.W.; Jeon, J.E.; Lim, C.; Lee, H.S.; Sim, C.J.; Oh, K.B.; Shin, J. Haliclonin a, a new macrocyclic diamide from the sponge Haliclona sp. Org. Lett. 2009, 11, 1713–1716.
[7]
Timm, C.; Mordhorst, T.; K？ck, M. Synthesis of 3-alkyl pyridinium alkaloids from the arctic sponge Haliclona viscosa. Mar. Drugs 2010, 8, 483–497.
[8]
Sakai, R.; Higa, T.; Jefford, C.W.; Bernardinelli, G. Manzamine a, a novel antitumor alkaloid from a sponge. J. Am. Chem. Soc. 1986, 108, 6404–6405.
[9]
Barrow, R.; Capon, R. Alkyl and alkenyl resorcinols from an australian marine sponge, Haliclona sp. (haplosclerida : Haliclonidae). Aust. J. Chem. 1991, 44, 1393–1405.
[10]
Sheikh, Y.M.; Djerassi, C. Steroids from sponges. Tetrahedron 1974, 30, 4095–4103.
[11]
Wang, G.Y.S.; Abrell, L.M.; Avelar, A.; Borgeson, B.M.; Crews, P. New hirsutane based sesquiterpenes from salt water cultures of a marine sponge-derived fungus and the terrestrial fungus Coriolus consors. Tetrahedron 1998, 54, 7335–7342, doi:10.1016/S0040-4020(98)00398-6.
[12]
Rashid, M.A.; Gustafson, K.R.; Boswell, J.L.; Boyd, M.R. Haligramides a and b, two new cytotoxic hexapeptides from the marine sponge Haliclona nigra. J. Nat. Prod. 2000, 63, 956–959.
[13]
Nuzzo, G.; Ciavatta, M.L.; Villani, G.; Manzo, E.; Zanfardino, A.; Varcamonti, M.; Gavagnin, M. Fulvynes, antimicrobial polyoxygenated acetylenes from the mediterranean sponge Haliclona fulva. Tetrahedron 2012, 68, 754–760.
[14]
Shin, J.; Seo, Y.; Cho, K.W.; Rho, J.R.; Paul, V.J. Osirisynes A-F, highly oxygenated polyacetylenes from the sponge Haliclona osiris. Tetrahedron 1998, 54, 8711–8720.
[15]
D’Auria, M.V.; Paloma, L.G.; Minale, L.; Riccio, R.; Zampella, A.; Debitus, C. Metabolites of the new caledonian sponge Claodocroce incurvata. J. Nat. Prod. 1993, 56, 418–423.
[16]
Diedrich, C.; Grimme, S. Systematic investigation of modern quantum chemical methods to predict electronic circular dichroism spectra. J. Phys. Chem. A 2003, 107, 2524–2539, doi:10.1021/jp0275802.
[17]
Laville, R.; Genta-Jouve, G.; Urda, C.; Fernández, R.; Thomas, O.P.; Reyes, F.; Amade, P. Njaoaminiums A, B, and C: Cyclic 3-alkylpyridinium salts from the marine sponge Reniera sp. Molecules 2009, 14, 4716–4724, doi:10.3390/molecules14114716.
[18]
Pescitelli, G.; Kurtán, T.; Krohn, K. Assignment of the Absolute Configurations of Natural Products by Means of Solid-State Electronic Circular Dichroism and Quantum Mechanical Calculations. In Comprehensive Chiroptical Spectroscopy; John Wiley & Sons, Inc.: Hoboken, NJ, USA, 2012; pp. 217–249.
[19]
Goto, H.; Osawa, E. Corner flapping: A simple and fast algorithm for exhaustive generation of ring conformations. J. Am. Chem. Soc. 1989, 111, 8950–8951.
[20]
Goto, H.; Osawa, E. Further developments in the algorithm for generating cyclic conformers. Test with cycloheptadecane. Tetrahedron 1992, 33, 1343–1346.
[21]
Goto, H.; Osawa, E. An efficient algorithm for searching low-energy conformers of cyclic and acyclic molecules. J. Chem. Soc. Perkin Trans. 2 1993, 2, 187–198.
Lee, C.; Yang, W.; Parr, R.G. Development of the colle-salvetti correlation-energy formula into a functional of the electron density. Phys. Rev. B 1988, 37, 785–789.
Stephens, P.J.; Harada, N. ECD cotton effect approximated by the gaussian curve and other methods. Chirality 2010, 22, 229–233.
[27]
Wang, G.Y.S.; Kuramoto, M.; Uemura, D.; Yamada, A.; Yamaguchi, K.; Yazawa, K. Three novel anti-microfouling nitroalkyl pyridine alkaloids from the okinawan marine sponge Callyspongia sp. Tetrahedron Lett. 1996, 37, 1813–1816.
[28]
Poulter, C.D.; Boikess, R.S.; Brauman, J.I.; Winstein, S. Shielding effects of a cyclopropane ring. J. Am. Chem. Soc. 1972, 94, 2291–2296.
[29]
Li, J.; Sha, Y. A convenient synthesis of amino acid methyl esters. Molecules 2008, 13, 1111–1119.
[30]
Henderson, G. A new look at carbonyl electronic transitions. J. Chem. Educ. 1990, 67, 392, doi:10.1021/ed067p392.
