Three Steroids with Unique Structural Feature of 5.BETA.-Spirostan-1.BETA.,3.BETA.,17.ALPHA.-trihydroxyl from Reineckia carnea

Abstract

Regular ArticleReineckia carnea (ANDR.) KUNTH belongs to the family Liliaceae, it is the only species of the genus Reineckia and indigenous to China and Japan.1) As a perennial ever-green herb, it can grow well on soils polluted by heavy metals and can produce a repairing effect on the soil that was polluted by copper.2) The Chinese name "ji xiang cao" means it can bring luck and fortune to people, especially when it was cultivated as ornamental plant and flowers. The whole plant has been used as an antitussive, an antarthritic, a hemostatic, and an antitode in traditional Chinese medicine.3) It is one of the most important ingredients of many medical prescriptions of Miao Minority in China and has been successfully developed into a medicine to treat cough and sore throats.4) The genus Reineckia is taxonomically close to Rohdea, Tupistra, Convallaria, Aspidistra, Liriope and Ophiopogon, and their chemical constituents are characterised by steroidal saponins with polyhydroxylated skeletons. [5][6][7][8][9] During the year 1955-1994, Japanese scholars reported some steroidal sapogenins and steroidal saponins from this plant. [10][11][12][13] The steroidal constituents from the underground parts of R. carnea exhibited inhibitory activity on cAMP phosphodiesterase and a potent inhibitor, showing almost equal IC 50 values compared to papaverine, was isolated.13) Formerly, we reported three spirostanol steroids from R. carnea:14) now, the 17a-OH derivatives of the three spirostanol steroids, corresponding to 25(S)-5b-spirostan-1b,3b,17a-triol (1), 25(S)-5b-spirostan-1b,3b,17a-were isolated from this plant. Compounds 1, 2, and 3 are the first naturally occurring steroids possessing unique structural feature of 5b-spirostan-1b,3b,17a-trihydroxyl. This paper describes the isolation and structural elucidation of these new compounds based on spectroscopic data and chemical transformation.Compound 1 C-NMR and distortionless enhancement by polarization transfer (DEPT) spectrum of 1 showed a quaternary carbon signal at d 110.6, which is the characteristic C-22 of a spirostanol skeleton. 17) On comparison between the 13 C-NMR spectrum of 1 with that of rhodeasapogenin [25(S)-5b-spirostan-1b,3b-diol], 14,18) the signal due to the C-17 carbon, which was observed at d 63.1 (CH) in rhodeasapogenin, appeared at d 89.6 as a quaternary carbon signal, accompanied by downfield shifts of the signals due to C-13 (ϩ5.5 ppm), C-16 (ϩ9.6 ppm), and C-20 (ϩ2.7 ppm) and upfield shifts of signals due to C-12 (Ϫ10.4 ppm), C-14 (Ϫ3.5 ppm), and C-21 (Ϫ5.9 ppm); in addition, the molecu-

New Phenylpropanoid Glycosides from Illicium majus and Their Radical Scavenging Activities

“…A comparison of the NMR spectral data of 3 with those of 2 ( Tables 1 and 2) indicated that both compounds 3 and 2 were similar, except for the sugar residue linked to C‐9 of the aglycone. The signals from the sugar moiety, including 2 anomeric signals at δ 4.38 (d, J =7.1) and δ 5.20 (d, J =1.2) in the 1 H‐NMR spectrum and 11 carbons signals at δ 102.2, 77.8, 77.5, 70.1, 65.5 and δ 100.9, 70.9, 70.8, 72.6, 68.5, 16.5 in the 13 C‐NMR spectra were in agreement with those of published work [13–15] . Thus, the sugar unit was identified as α‐L‐rhamnopyranosyl‐(1→2)‐β‐D‐xylopyranosyl.…”

A Steroidal Saponin RCE-4 Inhibits Lipopolysaccharide-Stimulated Inflammatory Responses via Blocking PI3K/Akt-Mediated Nf-κB Activation in RAW264.7 Cells

“…(rha, C-3"), 74.5 (rha, C-4"), 69.9 (rha, C-5"), 18.8 (rha, C-6"). These data were identical with (1β,3β,5β,25S)-spirostan-1,3-diol1-[α-L-rhamnopyranosyl-(1→2)-β-D-xylopyranoside] [10] (Fig. 1A).…”

Steroidal Glycosides from Reineckia carnea herba and Their Antitussive Activity

“…δ 6.8-14.4 for 5α-spirostane, δ 19.1-24.2 for 5β-spirostane) [7]. Different to 1, the broad singlet signal of H-1 (δ 3.92, brs) and H-3 (δ 4.40, br s) on the cis-fused A/B ring system were consistent with the 1β,3β-OH configuration [9]. In the NOESY plot, both H-3 and H-1 were correlated with α-oriented H-C (4) (δ 1.88), which was unambiguously assigned on the basis of the NOE correlation to H-C (9) (δ 1.35).…”