Trofosides A and B and Other Cytostatic Steroid-Derived Compounds from the Far East Starfish Trofodiscus Über

E. V. Levina^1 #, A. I. Kalinovsky¹, P. V. Andriyashchenko¹, N. I. Menzorova¹ and P. S. Dmitrenok¹

^#Fax: (4232) 314-050; e-mail: levina@piboc.dvo.ru

¹Pacific Institute of Bioorganic Chemistry, Far East Division, Russian Academy of Sciences, pr. 100-letiya Vladivostoka 159, Vladivostok, 690022, Russia

Received: April  28. 2006;  in final form: May  10, 2006

Abstract.  Three new polar steroids identified as trofoside A, (20R,24S)-24-O-(3-O-methyl-β-D-xylopyranosyl)-3β,6α,8,15β,24-pentahydroxy-5α-cholestane, its 22(23)-dehydro derivative (trofoside B), and 15-sulfooxy-(20R,24S)-5α-cholestane-3β,6β,8,15α,24-pentaol sodium salt, were isolated fromTrofodiscus über starfish extracts collected in the Sea of Ohotsk. Two known compounds, trofoside A aglycone, (20R,24S)-3β,6α,8,15β,24-pentahydroxy-5α-cholestane, and triseramide, (20R,24R,25S,22E)-24-methyl-3β6α,8,15β-tetrahydroxy-5α-cholest-22-en-27-oic acid (2-sulfoethyl)amide sodium salt, were also found. The structures of the isolated polyoxysteroids were established from their spectra. Minimal concentrations causing degradation of unfertilized egg-cells of the sea-urchin Strongylocentrotus intermedius(C _min) and terminating the cell division at the stage of the first division (C _min embr.), as well as the concentrations causing 50% immobilization of sperm cells (OC₅₀) and inhibiting their ability to fertilize egg-cells by 50% (IC₅₀) were determined for the isolated compounds. Of three compounds highly toxic in embryos and sea-urchin sperm cells, the polyol with a sulfo group in the steroid core was the most active; two glycosides with monosaccharide chains located at C3 and C24 atoms were less toxic. Note that all the compounds with the spermiotoxic activities differently affected the embryo development. The positions of monosaccharide residues in the core considerably influence the compound activity. For example, both mono-and double chained glycosides with the monosaccharide fragment at C3 and fragments at C3 and C4 atoms are active against sea-urchin sperm cells and embryos, whereas the C24 glycosylated trofoside A does not affect embryos and displays a poor spermiotoxicity.

Key words:  MALDI TOF mass spectra, NMR spectra, polyhydroxysteroids, starfish, Trofodiscus über

Russian Journal of Bioorganic Chemistry 2007, 33 (3): 334-340