Triterpene Glycosides from the Sea Cucumber Eupentacta Fraudatrix . Structure and Biological Action of Cucumariosides I 1,I 3,I 4,Three New Minor Disulfated Pentaosides
Free accessResearch articleFirst published online August, 2013
Triterpene Glycosides from the Sea Cucumber Eupentacta Fraudatrix . Structure and Biological Action of Cucumariosides I 1,I 3,I 4,Three New Minor Disulfated Pentaosides
Three new minor triterpene glycosides, cucumariosides I1 (1), I3 (2) and I4 (3) have been isolated from the Far Eastern sea cucumber Eupentacta fraudatrix. Structures of the glycosides were elucidated by 2D NMR spectroscopy and MS. Glycosides 1–3 belong to the group of cucumariosides I, having branched pentasaccharide carbohydrate moieties with two sulfate groups and possessing 3-O-methyl-D-xylose as a terminal monosaccharide unit that is a characteristic feature of all the glycosides isolated from E. fraudatrix. Glycosides 1 and 2 differ from each other by the side chain structures in the holostane aglycone moieties, while cucumarioside I4 (3) has a 23,24,25,26,27-pentanorlanostane aglycone with an 18(16)-lactone. Cytotoxic activities of glycosides 1–3 against mouse spleen lymphocytes and ascite form of mouse Ehrlich carcinoma cells, along with hemolytic activity against mouse erythrocytes and antifungal activity were studied. Glycoside 1, having an aglycone side chain with a 24(25)-double bond, possesses moderate activity in all the tests, while glycoside 2, having 23(24)-double bond and 25-hydroxy group in the side chain, and glycoside 3 with an aglycone with an 18(16)-lactone and shortened side chain have either low activity or are non-active.
SilchenkoA.S., KalinovskyA.I., AvilovS.A., AndryjaschenkoP.V., DmitrenokP.S., YurchenkoE.A., KalininV.I. (2012) Structures and cytotoxic properties of cucumariosides H2, H3, and H4 from the sea cucumber Eupentacta fraudatrix. Natural Product Research, 26, 1765–1774.
2.
SilchenkoA.S., KalinovskyA.I., AvilovS.A., AndryjaschenkoP.V., DmitrenokP.S., YurchenkoE.A., KalininV.I. (2011) Structure of cucumariosides H5, H6, H7 and H8, triterpene glycosides from the sea cucumber Eupentacta fraudatrix and unprecedented aglycone with 16,22-epoxy-group. Natural Product Communications, 6, 1075–1082.
3.
SilchenkoA.S., KalinovskyA.I., AvilovS.A., AndrijaschenkoP.V., DmitrenokP.S., MartyyasE.A., KalininV.I. (2012) Triterpene glycosides from the sea cucumber Eupentacta fraudatrix. Structure and biological action of cucumariosides A1, A3, A4, A5, A6, A12 and A15, seven new minor non-sulfated tetraosides and unprecedented 25-keto-27-nor-holostane aglycone. Natural Product Communications, 7, 517–525.
4.
SilchenkoA.S., KalinovskyA.I., AvilovS.A., AndrijaschenkoP.V., DmitrenokP.S., MartyyasE.A., KalininV.I. (2012) Triterpene glycosides from the sea cucumber Eupentacta fraudatrix. Structure and cytotoxic action of cucumariosides A2, A7, A9, A10, A11, A13 and A14, seven new minor non-sulfated tetraosides and an aglycone with an uncommon 18-hydroxy group. Natural Product Communications, 7, 845–852.
5.
SilchenkoA.S., KalinovskyA.I., AvilovS.A., AndrijaschenkoP.V., DmitrenokP.S., MartyyasE.A., KalininV.I. (2012) Triterpene glycosides from the sea cucumber Eupentacta fraudatrix. Structure and biological activity of cucumariosides B1 and B2, two new minor non-sulfated unprecedented triosides. Natural Product Communications, 7, 1157–1162.
6.
SilchenkoA.S., KalinovskyA.I., AvilovS.A., AndryjaschenkoP.V., DmitrenokP.S., MenchinskayaE.S., AmininD.L., KalininV.I. (2013) Structure of cucumarioside I2 from the sea cucumber Eupentacta fraudatrix (Djakonov et Baranova) and cytotoxic and immunostimulatory activities of this saponin and relative compounds. Natural Product Research, http://dx.doi.org/10.1080/14786419.2013.778851, in press.
7.
AfyatullovS.S., TishchenkoL.Y., StonikV.A., KalinovskyA.I, ElyakovG.B. (1985) Structure of cucumarioside G1 – new triterpene glycoside from the sea cucumber Cucumaria fraudatrix. Khimiya Prirodnykh Soedinenii, 2, 244–248.
8.
ShashkovA.S., ChizhovO.S. (1976) 13C NMR spectroscopy in chemistry of carbohydrates and relative compounds. Bioorganicheskaya Khimiya, 2, 437–491.
9.
AfyatullovS.S., KalinovskyA.I, StonikV.A. (1987) Structures of cucumariosides C1 and C2 – two new triterpene glycosides from the sea cucumber Eupentacta fraudatrix. Khimiya Prirodnykh Soedinenii, 6, 831–837.
10.
KalininV.I., AfyatullovS.S., KalinovskyA.I. (1988) Triterpene glycosides of the sea cucumber Eupentacta pseudoquinquesemita. Khimiya Prirodnykh Soedinenii, 2, 221–225.
11.
KalininV.I., AvilovS.A., KalinovskyA.I., StonikV.A., MilgromY.M., RashkesY.W. (1992) Cucumarioside G4 – new triterpene glycoside from the sea cucumber Eupentacta fraudatrix. Khimiya Prirodnykh Soedinenii, 6, 691–694.
12.
AvilovS.A., KalininV.I., MakarievaT.N., StonikV.A., KalinovskyA.I. (1994) Structure of cucumarioside G2, a novel nonholostane glycoside from the sea cucumber Eupentacta fraudatrix. Journal of Natural Products, 57, 1166–1171.
13.
AvilovS.A., AntonovA.S., DrozdovaO.A., KalininV.I., KalinovskyA.I., StonikV.A., RigueraR., LenisL.A., JimenezC. (2000) Triterpene glycosides from the Far-Eastern sea cucumber Pentamera calcigera. 1. Monosulfated glycosides and cytotoxicity of their unsulfated derivatives. Journal of Natural Products, 63, 65–71.
14.
AvilovS.A., AntonovA.S., DrozdovaO.A., KalininV.I., KalinovskyA.I., RigueraR., LenisL.A., JimenezC. (2000) Triterpene glycosides from the Far-Eastern sea cucumber Pentamera calcigera II: Disulfated glycosides. Journal of Natural Products, 63, 1349–1355.
15.
SilchenkoA.S., KalinovskyA.I., AvilovS.A., AndryjaschenkoP.V., DmitrenokP.S., KalininV.I., StonikV.A. (2012) 3β-O-Glycosylated 16p-acetoxy-9p-H-lanosta-7,24-diene-3p,18,20p-triol, an intermediate metabolite from the sea cucumber Eupentacta fraudatrix and its biosynthetic significance. Biochemical Systematics and Ecology, 44, 53–60.
16.
KalininV.I. (2000) System-theoretical (holistic) approach to the modelling of structural-functional relationships of biomolecules and their evolution: an example of triterpene glycosides from sea cucumbers (Echinodermata, Holothurioidea). Journal of Theoretical Biology, 206, 151–168.
