Triterpene Glycosides from the Sea Cucumber Eupentacta fraudatrix . Structure and Cytotoxic Action of Cucumariosides A 2,A 7,A 9,A 10,A 11,A 13 and A 14,Seven New Minor Non-Sulfated Tetraosides and an Aglycone with an Uncommon 18-Hydroxy Group
Free accessResearch articleFirst published online July, 2012
Triterpene Glycosides from the Sea Cucumber Eupentacta fraudatrix . Structure and Cytotoxic Action of Cucumariosides A 2,A 7,A 9,A 10,A 11,A 13 and A 14,Seven New Minor Non-Sulfated Tetraosides and an Aglycone with an Uncommon 18-Hydroxy Group
Seven new minor triterpene glycosides, cucumariosides A2 (1), A7 (2), A9 (3), A10 (4), A11 (5), A13 (6) and A14 (7) have been isolated from the Far Eastern sea cucumber Eupentacta fraudatrix. Structures of the glycosides were elucidated by 2D NMR spectroscopy and MS. Glycosides 1–7 belong to the group of cucumariosides A, having linear tetrasaccharide carbohydrate moieties without any sulfate group and possessing 3-O-methyl-D-xylose as a terminal monosaccharide unit. Glycosides 1, 2, 5-7 differ from each other in side chain structures in aglycone moieties, while cucumarioside A10 (4) has a 23,24,25,26,27-pentanorlanostane aglycone with 18(16)-lactone. Cucumarioside A9 (3), having an uncommon 18-hydroxy group, is the second representative of the unique metabolically active glycosides that are regarded as intermediates of glycoside biosynthesis in sea cucumbers. Cytotoxic activities of glycosides 1–7 and cucumarioside A8 (8) against mouse spleen lymphocytes and the cells of the ascite form of mouse Ehrlich carcinoma, along with hemolytic activity against mouse erythrocytes and antifungal activity were studied. Cucumariosides A2 (1), A8 (8) and A13 (6) demonstrated high hemolytic activities. Glycosides 1, 4 and 6 showed moderate cytotoxic activity. Only cucumarioside A8 (8), having an 18-oxymethylene group and a 24(25)-double bond, was very active in all the tests.
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-norholostane aglycone. Natural Product Communications, 7, 517–525.
2.
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.
3.
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.
4.
KalininV.I., AvilovS.A., KalinovskyA.I., StonikV.A. (1992) Cucumarioside G3 – minor triterpene glycoside from the sea cucumber Eupentacta fraudatrix. Khimiya Prirodnykh Soedinenii, 5, 729–730.
5.
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.
6.
BhatnagarS., DudoetB., AhondA., PoupatC., ThoisonO., ClastresA., LaurentD., PotierP. (1985) Invertebres marins du lagon neocaledonien IV. Saponines et sapogenines d'une holothurie, Actinopyga flammea. Bulletin de la Societe Chimique de France, 1, 124–129.
7.
AntonovA.S., AvilovS.A., KalinovskyA.I., AnastyukS.D., DmitrenokP.S., KalininV.I., TaboadaS., BoshA., AvilaC., StonikV.A. (2009) Triterpene glycoasides from Antarctic sea cucumbers. 2. Structure of achlioniceosides A1, A2 and A3 from the sea cucumber Achlionice violaescupidata (=Rhipidothuria racowitzai). Journal of Natural Products, 72, 33–38.
8.
SecoJ.M., QuinoaE., RigueraR. (2004) The assignment of absolute configuration by NMR. Chemical Reviews, 104, 17–117.
9.
SilchenkoA.S., KalinovskyA.I., AvilovS.A., AndryjashchenkoP.V., DmitrenokP.S., KalininV.I., StonikV.A. (2012) 3β-O-Glycosylated 16β-acetoxy-9β-H-lanosta-7,24-diene-3β,18,20β-triol, an intermediate metabolite from the sea cucumber Eupentacta fraudatrix (Echinodermata: Holothuroidea) and its significance for understanding the biosynthesis of 4,4,14-trimethylsterol glycosides, key natural products in the chemotaxonomy of sea cucumbers. Biochemical Systematics and Ecology, 44, 53–60.
10.
SilchenkoA.S., AvilovS.A., AntonovA.S., KalinovskyA.I., DmitrenokP.S., KalininV.I., StonikV.A., WoodwardC., CollinP.D. (2005) Glycosides from the sea cucumber Cucumaria frondosa III. Structure of frondosides A2-1, A2-2, A2-3 and A2-6, four new minor monosulfated triterpene glycosides. Canadian Journal of Chemistry, 83, 21–27.
11.
KalininV.I., AmininD.L., AvilovS.A., SilchenkoA.S., StonikV.A. (2008) Triterpene glycosides from sea cucucmbers (Holothurioidae, Echinodermata), biological activities and functions In Studies in Natural Product Chemistry (Bioactive Natural Products), Atta-ur-Rahman (Ed.). Elsevier Science Publisher, Netherlands, 35, 135–196.
