Clintoniosides A – C, New Polyhydroxylated Spirostanol Glycosides from the Rhizomes of Clintonia udensis

Abstract

Phytochemical analyses were carried out on the rhizomes of Clintonia udensis (Liliaceae) with particular attention paid to the steroidal glycoside constituents, resulting in the isolation of three new polyhydroxylated spirostanol glycosides, named clintonioside A (1), B (2), and C (3). On the basis of their spectroscopic data, including 2D-NMR spectroscopy, in combination with acetylation and hydrolytic cleavage, the structures of 1 -3 were determined to be (1b,3b,23S,24S,25R)-1,23,24-Introduction. -Clintonia udensis Trautv. et C. A. Mey. is a perennial plant belonging to the family Liliaceae, and is distributed in northeast China, the Korean Peninsula, and Japan. The rhizomes of C. udensis have long been used in traditional Chinese medicine for the treatment of blow and fatigue [1], and a few steroidal sapogenins such as diosgenin and heloniogenin have been detected in the plant [2] [3]. As part of our continuing investigation of plants of the family Liliaceae [4 -8], a phytochemical analysis of the rhizomes of C. udensis was conducted, special attention being paid to the steroidal glycoside constituents, which resulted in the isolation of three new polyhydroxylated spirostanol glycosides, named clintonioside A (1), B (2), and C (3). This article reports the structure determination of the new compounds on the basis of their spectroscopic data, including 2D-NMR spectroscopy, in combination with acetylation and hydrolytic cleavage.

Trifasciatosides A–J, Steroidal Saponins from <i>Sansevieria trifasciata</i>

“…[25][26][27] Further inspection of the 13 C-NMR data of the sugar moiety in comparison with those reported in the literature showed that xylose and rhamnose, were attached to the C-3′ and C-2′ positions of the inner glucose, respectively, which in turn was attached to the C-1 position of the aglycone as in compounds 1 and 2. 18) This was also supported by the results of acid hydrolysis and the downfield shifts observed for C-1 (δ 84.7), C-3′ (δ 88.5), and C-2′ (δ 76.0). Compound 3 was then elucidated as (…”

Novel steroidal saponins from Dioscorea esculenta (Togedokoro)

“…In particular, the observed HMBC cross-peaks (H1α and C19; H19 and C1) indicated that the hydroxyl group was coupled with the C1 of spirostane aglycone, and the configuration was determined as β by the coupling constant (J = 11.6, 6.1, and 4.8 Hz) of H1α and good agreement with those of clintonioside A. 23) In the NOESY spectrum, H1α also correlated with H3α and H9α. The HMBC cross-peak between H1′ and C3 proved that the glucopyranose was coupled with C3 of spirostane aglycone.…”

Chemical Composition and Biological Activity of Paris quadrifolia L.

“…The quaternary carbon atoms were identifi ed using the assigned protonated carbon resonances by means of a long-range proton-carbon correlation experiment (HMBC). By comparison with literature data (Mimaki and Watanabe, 2008;Takaashi et al, 1995) the aglycon was identifi ed as (1β,3β,23S,24S)-spirosta-5,25(27)-diene-1,3,21,23,24-pentol. The 1 H and 13 C NMR signals are listed in Table I.…”

“…Due to the characteristic downfi eld shifts of C-1 and C-24 that were observed at δ C 84.5 and 83.1 ppm, respectively, glycosidic linkages in these positions could be assumed. Furthermore, the downfi eld shift of C-21 (δ C 69.5 ppm) in comparison with δ C 62.2 ppm for non-substituted derivatives (Mimaki and Watanabe, 2008) suggested a third glycosidation in this position.…”