Fallaxosides C₁, C₂, D₁ and D₂, Unusual Oligosulfated Triterpene Glycosides from the Sea Cucumber Cucumaria fallax (Cucumariidae, Dendrochirotida, Holothurioidea) and Taxonomic Status of this Animal

Abstract

Four new triterpene glycosides, fallaxosides C1 (1), C2 (2), D1 (3) and D2 (4) along with the known cucumarioside A3-2 (5) and koreoside A (6) have been isolated from the sea cucumber Cucumaria fallax (Cucumariidae, Dendrochirotida). Structures of the glycosides have been elucidated by 2D NMR spectroscopy and mass spectrometry. All of the glycosides are rare non-holostane derivatives having shortened side chains and contain pentasaccharide carbohydrate moieties with two or three sulfate groups. Structures of these triterpene glycosides and their comparison with those earlier isolated from Cucumaria spp. and Pseudocnus dubiosus leoninus allow us to suggest that the present assignment of C. fallax to the genus Pseudocnus is not correct, and this species should be assigned to the genus Cucumaria. Cytotoxic activity of glycosides 1–5 against the ascite form of mouse Ehrlich carcinoma cells and mouse spleen lymphocytes and hemolytic activity against mouse erythrocytes have been studied. The glycosides were expectedly not active in all the tests due to the absence of an 18(20)-lactone in their aglycones and the presence of several sulfate groups. There was one exception, cucumarioside A3-2 (5), which demonstrated a weak cytotoxicity against lymphocytes and moderate hemolytic activity.

Triterpene Glycosides from the Far Eastern Sea Cucumber Thyonidium (=Duasmodactyla) kurilensis (Levin): The Structures, Cytotoxicities, and Biogenesis of Kurilosides A3, D1, G, H, I, I1, J, K, and K1

“…The 13 C NMR spectra of the carbohydrate chains of kuriloside K 1 (9) and kuriloside K (8) demonstrated their coincidence (Table 8) due to the presence of the same pentasaccharide, branched by C-4 Xyl1, sugar parts with the sulfate groups at C-6 Glc3 and C-6 Glc4. The analysis of the NMR spectra of the aglycone part of 9 indicated the presence of 22,23,24,25,26,27-hexa-nor-lanostane aglycone with 16β-acetoxy,(20S)-hydroxy-fragment (Table 7), identical to that of kuriloside J (7).…”

“…As a continuation of our investigation of glycoside composition of the sea cucumber Thyonidium (=Duasmodactuyla) kurilensis (Levin), we report herein the isolation and structure elucidation of nine glycosides, kurilosides A 3 (1), D 1 (2), G (3), H (4), I (5), I 1 (6), J (7), K (8), and K 1 (9) as well as two desulfated derivatives, DS-kuriloside L (10) and DS-kuriloside As a continuation of our investigation of glycoside composition of the sea cucumber Thyonidium (=Duasmodactuyla) kurilensis (Levin), we report herein the isolation and structure elucidation of nine glycosides, kurilosides A3 (1), D1 (2), G (3), H (4), I (5), I1 (6), J (7), K (8), and K1 (9) as well as two desulfated derivatives, DS-kuriloside L (10) and DS-kuriloside M (11). The animals were collected near Onekotan Island in the Sea of Okhotsk.…”

“…Table 7. 13 C and 1 H NMR chemical shifts, HMBC, and ROESY correlations of the aglycone moiety of kuriloside J (7) and K 1 (9). 8), showed that kuriloside K (8) has branching at C-4 Xyl1 in the disulfated pentasaccharide chain with the sulfate groups at C-6 Glc3 and C-6 Glc4.…”

Two novel holostane-type glycosides from the viscera of sea cucumber Apostichopus japonicus with antitumor activities

“…The majority of the glycosides contain holostane-type aglycones-lanostane derivatives with 18(20)-lactone, as opposed to non-holostane aglycones-lanostane derivatives without 18(20)-lactone. [6][7][8][9] The carbohydrate chains of the glycosides are comprised of two to six monosaccharide units. Sea cucumber glycosides exhibit a wide spectrum of biological activities against cardiovascular diseases, tumors, fungal infections, and hypertension.…”

Sulfated Glycosides from the Sea Cucumbers Block Ca2+ Flow in Murine Neuroblastoma Cells

“…Liouvilloside A (1) was found first in the Antarctic sea cucumber Staurocucumis liouvillei [11] and consequently isolated and structurally identified from the sea cucumber Pseudocolochirus violaceus [12]. The structures of the glycosides 24 ( Figure 1) were elucidated using the complex analysis of 2D NMR spectra and confirmed by the mass-spectrometry [13][14][15]. All of the investigated glycosides have two or three sulfate groups in the tetra-or pentasaccharide carbohydrate chains.…”