Okinawan sponges

Several examples of the monocyclic isothiocyano sesquiterpenoids having the bisabolane (83) skeleton are known. Along with the hydrocarbon theonellin (84), isothiocyanate 86 and formamide 87 were obtained from the Okinawan sponge Theonella cf. swinhoei. It seems remarkable, but not unusual, that not only was the amide the major constituent, but the isonitrile 85 was the missing member of the triad [57], Relative stereostructures were indicated by NMR analysis of theonellin formamide (87) and its transformation products. 

Haterumadioxins A and B were isolated from the Okinawan sponge Plakortis lita. Haterumadioxin A 100 was evaluated against a human cancer cell line panel and found to be effective against a melanoma cancer cell line. An analysis of the results obtained... 

Maru, N., Koyama, T., Ohno, O., Yamada, K., and Uemura, D. (2010a). Sunabedine, a novel toxic bromotyrosine-derivative alkaloid from Okinawan sponge, order Verongida. ELeterocycles 82, 371-375. 

Teruya, T., Nakagawa, S., Koyama, T., Arimoto, H., Kita, M., and Uemura, D. (2004). Nakiterpiosin and nakiterpiosinone, novel cytotoxic C-nor-D-homosteroids from the Okinawan sponge Terpios hoshinota. Tetrahedron 60, 6989-6993. 

The yellow pigment halenaquinol sulfate (410) has been isolated from the Okinawan sponge Xestospongia sapra and is a pentacyclic hydroquinone [345]. The absolute stereochemistry was determined to be 6S by comparing the CD spectrum of a derivative with a theoretically calculated spectrum [346]. Theoretical calculation of CD spectra of halenaquinol sulfate (410) isolated from X. exigua and X. sapra determined that the absolute stereostructure was 12bS [347]. The pentacyclic compound, xestoquinol sulfate (411) has been isolated from an Okinawan collection of X. sapra and its structure was elucidated on the basis of spectroscopic data and a chemical conversion [348]. 

Steroids from the Okinawan sponge Xestospongia sp., aragusteroketal C (71) and aragusterol C (72), exhibit potent cytotoxic activities against KB cells with IC50 values of 0.004 and 0.02 (ig/ml, respectively [63]. 

Tauroacidins A (194) and B (195) from an Okinawan sponge Hymeniacidon sp. exhibit inhibitory activity against EGF receptor kinase and c-erbB-2 kinase (IC50 20 pg/ml each) [155]. 

The thiol group can also be found in heterocyclic compounds such as 2-mercaptobenzothiazole (9) and echinoclathrine C (10). Compound 9 was isolated from the symbiont bacterium Micrococcus sp., which was obtained from the sponge Tedania ignis [13]. The pyridine alkaloid echinoclathrine C (10) and its S-acetylated derivative, echinoclathrine B (11), were isolated from the Okinawan sponge Echinoclathria sp. [14]. The position of the hydroxyl and acylamino group on the phenyl ring in echinoclathrines (11 and 10) was recently corrected [15]. Compound 11 showed weak immunosuppressive activity in the mixed lymphocyte reaction assay with an IC50 of 9.7 pg/ml [14]. 

The medicinal terrestrial plant Turraea pubescens has yielded turrapubesin A (637) (742), and the Okinawan sponge Ircinia sp. contains the new furanoses-terterpenes 638 and 639 (743). An Aspergillus sp. culture has yielded ICM0301C (640) and ICM0301D (641), along with several nonchlorinated analogs (744, 745). 

The Okinawan sponge Psammaplysilla purea that contains purealidins M-0 (2004-2006) also yields purealidins J (2078), K (2079), L (2080), P (2081), Q (2082), and R (2083) (1835). Purealidin J (2078) is the antipode of pseudocer-atinine A (2089). The Indian sponge Psammaplysilla purpurea, which is the source of purpurealidins F-H (2018-2020) and other bromotyrosines (vide supra), also contains purpurealidins A (2084), B (2085), C (2086), and D (2087) (1842). A Caribbean Pseudoceratina sponge has afforded the simple carboxylic acid 2088 (1868). The New Caledonian sponge Pseudoceratina verrucosa, which is the source of pseudoceratinine B (1990), also contains pseudo-ceratinines A (2089) and C (2090), the absolute configurations of which are shown (1829). 

Miyaoka H, Shimomura M, Kimura H, Yamada Y (1998) Antimalarial Activity of Kalihinol A and New Relative Diterpenoids from the Okinawan Sponge, Acanthella sp. Tetrahedron 54 13467... 

Teruya T, Nakagawa S, Koyama T, Suenaga K, Kita M, Uemura D (2003) Nakiterpiosin, a Novel Cytotoxic C-nor-D-Homosteroid from the Okinawan Sponge Terpios hoshinota. Tetrahedron Lett 44 5171... 

Takada N, Sato H, Suenaga K, Arimoto H, Yamada K, Ueda K, Uemura D (1999) Isolation and Structures of Haterumalides NA, NB, NC, ND, and NE, Novel Macrolides from an Okinawan Sponge Ircinia sp. Tetrahedron Lett 40 6309... 

Takada N, Watanabe R, Suenaga K, Yamada K, Ueda K, Kita M, Uemura D (2001) Zamamistatin, a Significant Antibacterial Bromotyrosine Derivative, from the Okinawan Sponge Pseudoceratina purpurea. Tetrahedron Lett 42 5265... 

A new cytotoxic sterol, bienmasterol, possessing the rare 22,25-diene side chain, has been isolated from the Okinawan sponge Bienma sp. 

Manzamines comprise a new group of /3-carboline alkaloids having polycyclic ring systems, the provenance of which is problematical as there appears to be no obvious biogenetic path. Manzamine A (180) was isolated from an Okinawan sponge (Haliclona sp.) and shown to exhibit antitumor activity. Its structure and absolute configuration were determined by X-ray analysis (150). From an Okinawan sponge (Pellina sp.) keramamines A (180) and B (181) were isolated as antimicrobial substances (151), and keramamine A was found to be identical with manzamine A. 

Further investigation of the Okinawan sponge Haliclona sp. resulted in the isolation of manzamines B-F (182-186), which show cytotoxic activity (152-154). The structures of manzamines B (182) and C (183) were based on X-ray analysis. Manzamine F (186) was found to be identical with keramamine B, the structure of which with a 1,2,3-triazacyclohexane moiety (181) was revised to structure 186 containing a hexahydro-5(2//)-azocinone ring. Total synthesis of manzamine C (183) was achieved by the... 

Macrocyclic quinolizidine or 1-oxaquinolizidine alkaloids, aragu-spongines B-H (236-242) and J (243) (206) and aragupetrosine A (244) (207) were isolated from an Okinawan sponge (Xestospongia sp.) together with the previously known petrosin (245) (208) and petrosin A (246) (209). These alkaloids show vasodilating activity. 

Mycalamides A (286) (233) and B (287) 234) were isolated from a New Zealand sponge of the genus Mycale and exhibit significant in vivo antiviral and antitumor activity. From an Okinawan sponge Theonella sp.) onna-mide A (288) with a structure closely related to mycalamides was isolated,... 

Niphatynes A (418) and B (419) are pyridine derivatives with alkyne and methoxylamine functionalities isolated from the Fijian sponge Niphates sp. (344). Niphatyne A (418) exhibits cytotoxic activity. Theonelladins A-D (420-423) are other pyridine alkaloids obtained from the Okinawan sponge Theonella swinhoei and exhibit antineoplastic activity (345). These... 

Kobayashi, J., Murayama, T., and Ohizumi, Y., Theonelladins A-D, novel antineoplastic pyridine alkaloids from the Okinawan sponge Theonella swinhoei, Tetrahedron Lett., 30, 4833, 1989. 

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