3β,5α,6β-Trihydroxylated Sterols with a Saturated Nucleus from Two Populations of the Marine Sponge Cliona copiosa

Compositions of Royal Jelly II. Organic Acid Glycosides and Sterols of the Royal Jelly of Honeybees (Apis mellifera)

“…In the HMBC spectrum, this quaternary carbon was correlated with Ha-3 and H 3 -19. Further, the signals of Ha-3 (ϩ0.85 ppm), Hb-4 (ϩ0.96 ppm), and H 3 -19 (ϩ0.50 ppm) showed the typical pyridine-induced deshielding effect 14,15) due to 1,3-diaxial interactions (d pyridine-d 5 Ϫd CDCl 3 : CD 3 OD(9 : 1) with the C-5 and C-6 hydroxyl groups, confirming a 3b,5a,6b-trihydroxyl configuration. From these findings, together with comparison of 1 H-NMR spectroscopic data with the corresponding signals of compounds (16,17) with the same steroid ring skeleton, the structure of 6 was characterized as (24Z)-stigmast-24(28)-ene-3b,5a,6b-triol (Fig.…”

“…Both fractions were further separated with HPLC including a recycling mode, and two (1, 2) from the former and 16 (3-18) compounds from the latter were isolated in pure form. Among them, compounds 7-18 were identified as the known sterols 24-methylenecholesterol (7), 8) isofucosterol (8), 9) cholesta-5,24(24Ј)-dien-3b-ol-7-one (9), 10,11) cholesta-5,24(24Ј)-diene-3b,7b-diol (10), 10,12) cholesta-5,24(24Ј)-diene3b,7a-diol (11), 10,12) b-sitosterol (12), 13) stigmast-5-en-3b-ol-7-one (13), 13) stigmast-5-ene-3b,7b-diol (14), 13) stigmast-5-ene-3b,7a-diol (15), 13) cholest-24(24Ј)-ene-3b,5a,6b-triol (16), 14) stigmastane-3b,5a,6b-triol (17), 15) and desmosterol (18) 16) by comparison of their 1 H-and 13 C-NMR spectroscopic data with those described in the literature. …”

“…5,24(24Ј)-diene-3b,7b-diol (10), 10,12) cholesta-5,24(24Ј)-diene3b,7a-diol (11), 10,12) b-sitosterol (12), 13) stigmast-5-en-3b-ol-7-one (13), 13) stigmast-5-ene-3b,7b-diol (14), 13) stigmast-5-ene-3b,7a-diol (15), 13) cholest-24(24Ј)-ene-3b,5a,6b-triol (16), 14) stigmastane-3b,5a,6b-triol (17), 15) and desmosterol (18) 16) by comparison of their 1 H-and 13 C-NMR spectroscopic data with those described in the literature.…”

New 3.BETA.,5.ALPHA.,6.BETA.-Trihydroxysteroids from the Octocorals Bebryce sp. (Plexauridae) and Carijoa sp. (Clavulariidae)

“…The remaining hydroxy group at C-5, as indicated by analysis of HMBC correlations and characteristic NMR signals analysis. It was found that the structure of 1 was very similar with those of a known steroid, (22E)-5a-cholest-22-ene3b,5,6b-triol, 7) excepting that less one sp 3 methylene unit was found in 1 (nine sp 3 methylene units were found in (22E)-5a-cholest-22-ene-3b,5,6b-triol) and this observation was supported by comparing the spectral data of 1 with those of another known steroid, halistanol sulfate E, 10) which possesses the same side chain (from C-20 to C-26) as that of 1. Based on the above findings, the structure of 1 was established.…”

New polyhydroxylated steroid from the South China Sea gorgonianAnthogorgia caerulea

“…Polyoxygenated steroids with a 3�,5�,6�-trihydroxy moiety are frequently encountered in marine organisms, such as in gorgonian corals (Qiu, Qi, Zhang, Yang, & Xiao, 2006;Shen, Prakash, & Chang, 2001;Tanaka et al, 2002), soft corals (Chang, Wen, Wang, & Duh, 2008;Ramesh & Venkateswarlu, 1999;Umeyama, Shoji, Ozeki, & Arihara, 1996), sponges (Notaro, Piccialli, & Sica, 1991;Rao et al, 2010) and starfishes (Iorizzi, 1995;Roccatagliata, Maier, & Seldes, 1995). It was reported that steroids with the 3,5,6-trihydroxy moiety might arise biogenetically from the corresponding D 5,6 -steroids (Notaro et al, 1991). Among the polyoxygenated steroids (1-7), three of them (1, 2 and 5) possess �-or �-OH-11.…”