Steroids from Starfish

As the glycosides from starfish are steroidal in nature and as some known polyhydroxylated steroids with moderate cytotoxicity have been isolated from these animals, the literature since 1980 dealing with such compounds will be reviewed here. Aside from some monohydroxyste-rols from Echinaster sepositus 646), Acanthaster planci 647) - this being a source of a new cyclopropane sterol Asterias vulgaris 648), and Comasterias lurida 649), the reports deal mainly with polyhydroxylated steroids. 

Minale et al. investigated the starfish species Protoreaster nodosus 617, 650, 651), Hacelia attenuata 617, 626, 652), and Luidia maculata 653). Structure determination of these compounds, isolated from the methanol or chloroform-methanol extracts was based upon H- and 

D Auria et al. (654) found two groups of sterol sulfates in the aqueous extract of the starfish Euretaster insignis. Hydrolysis of the less polar fraction gave cholest-7-en-3 P-ol and C26 C27, C28, and C29 5a-steroidal alcohols. The more polar fraction contained sulfated 3p,21-dihydroxysteroids. After solvolysis to remove the sulfate groups the steroids were identified as (20i )-24-methylenecholestane-3P,21-diol (981), (20R)-24-methylenecholest-5-ene-3p,21-diol (982), (20/ ,22 )-24-methylcholest-22-ene-3P,21-diol (983), (20/ )-choles-tane-3p,21-diol (984), (207 ,22 )-cholest-22-ene-3p,21-diol (985), and (207 )-cholest-5-ene-3P,21-diol (986). This starfish was apparently devoid of saponins. 

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Stonik VA, Ivanchina NV, Kicha AA (2008) New polar steroids from starfish. Nat Prod Commun 3 1587-1610... 

Minale, L., C. Pizza, F. Zollo, and R, Riccio Trace Polyhydroxylated Steroids from Starfish Hacelia attenuata. J. Nat. Prod. 46, 736 (1983). 

Polyoxygenated marine steroids from the deep water starfish Styracaster caroli. J. Nat. Prod., 57,1361 -73. 

Levina, E.V. Andriyashchenko, P.V. Kalinovsky, A.I. Stonik, V.A. (1998) New ophiuroid-type steroids from the starfish Pteraster tesselatm. J. Nat. Prod., 61, 1423-6. 

Iorizzi, M., de Riccardis, F., Minale, L., Palagiano, E., Riccio, R., Debitus C., and Duhet, D., Polyoxygenated marine steroids from the deep water starfish Styracaster caroli, J. Nat. Prod., 57, 1361, 1994. 

Iorizzi, M., De Marino, S., Minale, L., Zollo, F., Le Bert, V., and Roussakis, C., Investigation of the polar steroids from an Antarctic starfish of the family Echinasteridae isolation of 27 polyhydroxys-teroids and steroidal oligoglycosides, Tetrahedron, 52, 10997, 1996. 

Several reviews on steroidal glycosides from starfishes with descriptions of their stmctures, distribution and spectroscopic characteristics have been published [10, 18, 19]. 

Much work has been done in the last thirty years on the isolation and structural characterization of saponins and polyhydroxylated steroid glycosides from starfishes and sea cucumbers. The wide spectrum of biological activities these compounds show must be related to their role in the organisms that produce them and this task must be addressed in future investigations. 

I. Bruno, L. Minale, and R. Riccio, Starfish saponins, part 43. Structures of two new sulfated steroidal fucofuranosides (imbricatosides A and B) and six new polyhydroxysteroids from starfish Dermasterias imbricata, J. Nat. Prod., 53 (1990) 366-374. 

Fig. 4. Glycosides of polyhydroxysteroids and related polar steroids from the starfish Coscinasterias tenuispina (55).

Fig. 14, Higly hydroxylated steroids from the starfish Archaster typicus (124 - 126).

Four new steroid glycosides containing a 6-deoxy-P-D-glucose 4-sulfate moiety have been isolated from starfish. ... 

During our work on active metabolites from starfish we have isolated from Astropecten indicus three novel steroidal glycosides named as indicoside A (26). B (27) and C (28). The red alga Laurencia pinnatifida yielded three new halogenated sesquiterpenoids pinnatificine (29) pinnatifidone (30) and 1(1 4(3,10d tr ibromo-3-chloro-7(14)-ene-a-chamigrene (31). ... 

Several steroidal saponin sulfates have been reported from starfish (Hostettmann, 1985). Sea cucumbers secrete water-soluble glycosides, holothurins, that possess greater hemolytic ability than saponins of plant origin. These compounds are mixtures of glycoside sulfates (Agarwal and Ras-togi, 1974). 

Minale, L., C. Pizza, R. Riccio, and F. Zollo Steroidal Glycosides from Starfishes. Pure Appl. Chem. 54, 1935 (1982). 

Starfish Saponins. Part 10. Further 24-0-Glycosidated Steroids from the... 

Riccio, R., L. Minale, S. Pagonis, C. Pizza, F. Zollo, and J. Pusset A Novel Group of Highly Hydroxylated Steroids from the Starfish Protoreaster nodosus. Tetrahedron 38, 3615 (1982). 

D Auria, M.V., E. Finamore, L. Minale, C. Pizza, R. Riccio, F. Zollo, M. Pusset, and P. Tirard Steroids from the Starfish Euretaster insignis a Novel Group of Sulphated 3p,21-Dihydroxysteroids. J. Chem. Soc., Perkin Trans. I 1984, 2277. 

De Riccardis, F., Minale, L, Ricdo, R., Giovanniti, B., lorizzi, M., and Debitus, C. (1993) Phosphated and sulfated marine polyhydroxylated steroids from the starfish Tremaster novaecakdoniae. Gazz. Chim. Ital, 122, 79-85. 

Higuchi, R., Noguchi, Y Komori, T., and Sasaki, T. (1988a) H-NMR Spectroscopy and biological activities of polyhydroxylated steroids from the starfish Asterina pectinifcra Muller et Trochel. Liebigs Ann. Chem., 1185-1189. 

Ivanchina, N.V., Kicha, A.A., Huong, T.T.T., Kalinovsky, A.I., Dmitrenok, P.S., Agafanova, I.G., Long, P.Q., and Stonik, V.A. (2010) Flighly hydroxylated steroids from the starfish Archaster typicus from the Vietnamese waters. Steroids, 75, 897-904. 

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