The isolation of lanosta-7,9(11),24-trien-3β,21-diol from the fungus ganoderma australe

The lipid-soluble fraction of the fungus Ganoderma australe belonging to the family Polyporaceae has yielded ergosterol palmitate, ergosta-7,22-dien-3-one, ergosterol and lanosta-7,9(11),24-trien-3β,21-diol. This fungus is the second reported natural source of the latter compound whose structure is now established on the basis of spectral data.     

Triterpenes in Ganoderma lucidum

Four new oxygenated triterpenes, isolated from the mycelia of the fungus Ganoderma lucidum, were determined to be lanosta-7,9(11),24-trien-3α, 15α-dihydroxy-26-oic acid, lanosta-7,9(11),24-trien-3β, 15α-dihydroxy-26-oic-acid, lanosta-7,9(11),24-trien-3β,22β-diacetoxy-15α-hydroxy-26-oic acid and lanosta-7,9(11),24-trien-15α,22β-diacetoxy-3β-hydroxy-26-oic acid by spectroscopic methods.     

23,24,25,26,27-Pentanorlanost-8-en-3β,22-diol from Verticillium lecanii

23,24,25,26,27-Pentanorlanost-8-en-3β,22-diol has been isolated from the mycelium of the fungus Verticillium lecanii. Addition of lanosterol to the culture medium did not significantly increase the yields either of the pentanorlanostane metabolites or of ergosterol.     

Isolation of Lanosta-8,25-dien-3β-ol from the fungus Fomes Fastuosus

A new lanostane triterpene has been isolated from the fungus Fomes fastuosus which causes wood-rotting of Emblica officinalis. The compound is assigned the structure lanosta-8,25-dien-3β-ol on the basis of spectral data and correlation with lanosterol.     

Three new oxygenated triterpenoids of the lupane series from Gymnosporia wallichiana

Two new epimeric triterpenoid acids, gymnosporic acid, 3β-hydroxy-(20R)-lupan-29-oic acid, wallichianic acid, 3β-hydroxy-(20S)-lupan-29-oic acid and a new diol wallichianol, (20S)-lupane-3β,29-diol have been isolated from Gymnosporia wallichiana, in addition to β-amyrin, friedelin, 3β-hydroxy-29-norlupan-20-one and dulcitol.     

Acacidiol,a new nor-triterpene from the sapogenins of Acacia concinna

From the neutral fraction of the acid hydrolysate of the saponin of Acacia concinna pods, acacic acid lactone 3β-acetate and a new nor-triterpene ‘acacidiol’ have been isolated. The latter is shown to be 28-noroleana-16,18-diene-3β,21β-diol.     

An unusual lanostane-type triterpenoid,spiroinonotsuoxodiol, and other triterpenoids from Inonotus obliquus

An unusual lanostane-type triterpenoid, spiroinonotsuoxodiol (1), and two lanostane-type triterpenoids, inonotsudiol A (2) and inonotsuoxodiol A (3), were isolated from the sclerotia of Inonotus obliquus. Their structures were determined to be (3S,7S,9R)-3,7-dihydroxy-7(8 → 9)abeo-lanost-24-en-8-one (1), lanosta-8,24-dien-3β,11β-diol (2), and (22R)-3β,22-dihydroxylanosta-8,24-dien-11-one (3) on the basis of NMR spectroscopy, including 1D and 2D (¹H–¹H COSY, NOESY, HMQC, HMBC) NMR, and FABMS. Compounds 1–3 showed moderate activity against cultured P388, L1210, HL-60 and KB cells.     

Ergosterol and its derivatives from Grifola frondosa inhibit antigen-induced degranulation of RBL-2H3 cells by suppressing the aggregation of high affinity IgE receptors

Grifola frondosa is an edible mushroom consumed as a health food and/or traditional medicine in Asia. However, the anti-allergic effects of G. frondosa are not yet understood. In this study, we demonstrated the effects of G. frondosa extract (GFE) on IgE-mediated allergic responses, using antigen-stimulated RBL-2H3 cells. Three active compounds: ergosterol, 6β-methoxyergosta-7,22-dien-3β,5α-diol (MEDD), and 6-oxoergosta-7,22-dien-3β-ol (6-OXO) were isolated from GFE and shown to inhibit the antigen-induced release of β-hexosaminidase and histamine. Among the three active components, we focused on ergosterol because of its high content in GFE. Ergosterol inhibited the aggregation of high-affinity IgE receptor (FcεRI), which is the first step in the activation of mast cells and antigen-induced tyrosine phosphorylation. Furthermore, ergosterol suppressed antigen-increased IL-4 and TNF-α mRNA. Taken together, our findings suggest that G. frondosa, including ergosterol and its derivatives as active components, has the potential to be a novel functional food that prevents type I allergies.     

Triterpenoids from Mangifera indica

From the neutral fraction of the n-hexane extract of stem bark of Mangifera indica, (var./cv Banganpalli) six new tetracyclic triterpenoids, cycloart-24-ene-3β,26-diol, the C-24 epimers of cycloart-25-ene-3β,24,27-triol, the C-24 epimers of cycloartane-3β,24,25-triol and 3-ketodammar-24E-ene-20S,26-diol together with the known compounds cycloartenol, α-amyrin, β-amyrin, sitosterol 3β-hydroxycycloart-25-en-26-al, dammarenediol II, the C-24 epimers of cycloart-25-ene-3β,24-diol, 24-methylenecycloartane-3β,26-diol, ψ-taraxastane-3β,20-diol and ocotillol II have been isolated. The acidic fraction of the same extract, on esterification with diazomethane followed by chromatography, yielded methyl mangiferonate, methyl isomangiferolate, methyl mangiferolate and the diazomethane adduct of methyl mangiferolate. The structures were elucidated by spectroscopic and chemical methods.     

omega-Hydroxylase for 5beta-cholestane-3alpha,7alpha-diol in the biosynthesis of chenodeoxycholic acid.

The 5β-cholestane-3α,7α-diol 26-hydroxylase system, which is involved in the conversion of cholesterol to chenodeoxycholic acid, was studied in rat liver mitochondria. 26-Hydroxylase of 5β-cholestane-3α,7α-diol showed the following characteristics. (i) 5β-Cholestane-3α,7α-diol 26-hydroxylase requires electron donors similar to those required for 5β-cholestane-3α,7α,12α-triol 26-hydroxylase. (ii) Both enzyme activities are inhibited by similar inhibitors such as carbon monoxide and phenylisocyanide, but not by respiratory inhibitors such as rotenone, amytal, antimycin A, and cyanide. (iii) The presence of 5β-cholestane-3α,7α-12α-triol in the incubation mixture for 5β-cholestane-3α,7α-diol inhibits the latter activity in a competitive manner. (iv) The distribution patterns of both enzyme activities in submitochondrial fractions are similar. (v) The reconstituted enzyme system composed of partially purified cytochrome P-450 from rat liver mitochondrial inner membrane, NADPH-adrenodoxin reductase and adrenodoxin (both purified from bovine adrenocortical mitochondria), and NADPH showed 26-hydroxylation activity not only for 5β-cholestane-3α,7α-diol but also for 5β-cholestane-3α,7α,12α-triol; both activities were comparable.     

Diterpenoids of Halimium viscosum

From the neutral fraction of the hexane extract of Halimium viscosum the following components were isolated; 7-labdene-3β,l5-diol, 15-acetoxy-7-labden-3β-ol and a new diterpene-lactone with a rearranged ent-labdane skeleton, 13S-ent-9, 1-friedo-labd-1(10)-en-15-acetoxy-2R,18-olide. From the non-saponifiable part, beside 7-labdene-3β, 15-diol and 7, 13E-labdadiene-3β, 15-diol, the new diterpene 8(17)-labdene-3β, 7α, 15-triol was extracted. The structures were elucidated by spectroscopic methods, correlations or synthesis.     

Androgens with activity at estrogen receptor beta have anxiolytic and cognitive-enhancing effects in male rats and mice

Testosterone (T) and its metabolites may underlie some beneficial effects for anxiety and cognition, but the mechanisms for these effects are unclear. T is reduced to dihydrotestosterone (DHT), which can be converted to 5α-androstane,3α,17β-diol (3α-diol) and/or 5α-androstane-3β,17β-diol (3β-diol). Additionally, T can be converted to androstenedione, and then to androsterone. These metabolites bind with varying affinity to androgen receptors (ARs; T and DHT), estrogen receptors (ERβ; 3α-diol, 3β-diol), or GABA_A/benzodiazepine receptors (GBRs; 3α-diol, androsterone). Three experiments were performed to investigate the hypothesis that reduced anxiety-like and enhanced cognitive performance may be due in part to actions of T metabolites at ERβ. Experiment 1: Gonadectomized (GDX) wildtype and ERβ knockout mice (βERKO) were subcutaneously (SC) administered 3α-diol, 3β-diol, androsterone, or oil vehicle at weekly intervals, and tested in anxiety tasks (open field, elevated plus maze, light–dark transition) or for cognitive performance in the object recognition task. Experiment 2: GDX rats were administered SC 3α-diol, 3β-diol, androsterone, or oil vehicle, and tested in the same tasks. Experiment 3: GDX rats were androsterone- or vehicle-primed and administered an antagonist of ARs (flutamide), ERs (tamoxifen), or GBRs (flumazenil), or vehicle and then tested in the elevated plus maze. Both rats and wildtype mice, but not βERKO mice, consistently had reduced anxiety and improved performance in the object recognition task. Androsterone was only effective at reducing anxiety-like behavior in the elevated plus maze and this effect was modestly reduced by flumazenil administration. Thus, actions at ERβ may be required for T's anxiety-reducing and cognitive-enhancing effects.     

Metabolic transformations of some ent-kaurenes in Gibberella fujikuroi

The conversion of ent-kaur-16-enes to gibberellic acid in Gibberella fujikuroi is blocked by A-ring modifications. Thus ent-3β-hydroxykaur-16-en-19-yl succinate gives good conversion (46%) to the 7β-hydroxy derivative.* Under the same conditions the 3β-epimer gives 7β- or 6α-hydroxylation and the former occurs for the 3-oxo analogue. The succinoyloxy function acts as a less efficient block and ent-kaur-16-en-19-yl succinate is converted to 7β-hydroxy and 6β,7β-dihydroxy derivatives along with gibberellic acid. Hydrolysis of the succinate block of the metabolities provides the 7β, 19-diol and 6β,7β, 19-triol. Of this pair only the former was effectively metabolized to gibberellic acid in G. fujikuroi.     

Terpenoid and biflavonoid constituents of Calophyllum calaba and Garcinia spicata from Sri Lanka

A new bark acid, isochapelieric acid (cis-chapelieric acid), chapelieric acid, friedelin, friedelan-3β-ol, canophyllal, canophyllol, friedelan-3β,28-diol, canophyllic acid and amentoflavone have been isolated and characterized from leaf extractives of Calophyllum calaba. ¹³CNMR spectra of methyl chapelierate and methyl isochapelierate have been recorded and interpreted. Leaf extractives of Garcinia spicata afforded an unidentified long chain carboxylic acid, friedelin, friedelan-3β-ol, sitosterol and the biflavanones GB-1, GB-1a, GB-2a and morelloflavone. Chemotaxonomic significance of the occurrence of some of the above foliar constituents in Calophyllum and Garcinia species is discussed.     

Stereospecific reduction of progesterone by Pisum sativum

[4 -¹⁴C]-Progesterone was applied to the leaves of growing pea plants, Pisum sativum. After 3 weeks, about 50% of the administered steroid was reduced, about 20% being reduced to 5α-pregnane-3α,20β-diol as the major metabolite. The radioactivities of 5α-pregnane-3α,20α-diol and 5α-pregnane-3α,20β-diol after 3 weeks were more than twice those after one week. The following radioactive metabolises were also isolated: 5α-pregnane-3,20-dione; 20α-hydroxy-4- pregnen-3-one; 20β-hydroxy-4-pregnen-3-one; 3α-hydroxy-5α-pregnan-20-one; 3α-hydroxy-5β-pregnan-20-one; 3β-hydroxy- 5α-pregnan-20-one; 20β-hydroxy-5α-pregnan-3-one; 5α-pregnane-3β,20β-diol; and 5β-pregnane-3α,20β-diol. The radioactivities of the 5α-pregnane derivatives were considerably higher than those of the corresponding 5β-pregnane derivatives.     

Triterpenoids of Salvia horminum,constitution of a new diol

Lupeol, lup-(20)29-ene-2α,3β-diol and a new triterpenic alcohol olean-(13)18-ene-2β,3β-diol were isolated from the petrol extract of air dried Salvia horminum and their structures were determined.     

Configurational studies on red algae carotenoids

The configurations of (6′R)-β,ε-carotene, (3′R,6′R)-β,ε-caroten-3′-ol (α-cryptoxanthin), (3R,3′R,6′R)-β,ε-carotene-3,3′-diol (lutein), (3R)-β,β-caroten-3-ol (β-cryptoxanthin), (3R,3′R)-β,β-carotene-3,3′-diol (zeaxanthin) and all-trans (3S,5R,6S,3′R)-5,6-epoxy-5,6-dihydro-β,β-carotene-3,3′-diol (antheraxanthin) were established by CD and ¹H NMR studies. The red algal carotenoids consequently possessed chiralities at each chiral center (C-3, C-5, C-6, C-3′, C-6′), corresponding to the chiralities established for the same carotenoids in higher plants. Two post mortem artifacts from Erythrotrichia carnea were assigned the chiral structures (3S,5R,8R,3′R)-5,8-epoxy-5,8-dihydro-β,β-carotene-3,3′-diol [(8R)-mutatoxanthin] and (3S,5R,8S,3′R)-5,8-epoxy-5,8-dihydro-β,β-carotene-3,3′-diol [(8S)-mutatoxanthin]. This is the first well documented report of a naturally occurring β,ε-caroten-3′-ol (¹H NMR, CD, chemical derivatization).     

Formation of a 5 hydroxy sterol by Saccharomyces cerevisiae

The incorporation of [28 ¹⁴C] ergosta-7,24(28)-dien-3β-ol into ergosta-7,22-dien-3β,5α-diol by aerobically growing $\text{S.}\text{cerevisiae}$ has established its presence in this organism. This, coupled with previous work, is considered to be substantive evidence for the operation of a hydroxylation-dehydration mechanism in the introduction of Δ⁵ unsaturation in ergosterol biosynthesis in yeast.     

The role of (25S)-5α-cholestan-3β, 26-diol and (25S)-5α-furostan-3β,26-diol in the biosynthesis of tomatidine and neotigogenin

(25S)-5α-Cholestan-3β,26-diol was incorporated into neotigogenin and tomatidine, and (25S)-5α-furostan-3β,26-diol only in neotigogenin,     

Chemical syntheses of 5α-cholesta-6,8(14)-dien-3β-ol-15-one and related 15-oxygenated sterols

Hydroboration of 5α-cholesta-8,14-dien-3β-ol (I) gave 5α-cholest-8-en-3β,15α-diol (IV) in 89% yield. 5α-Cholest-7-en-3β,15α-diol (V) was prepared in 91% yield by hydroboration of 5α-cholesta-7,14-dien-3β-ol (II). Hydroboration of 27:63 mixture of I and II gave IV and V in 18% and 70% yields, respectively. 5α-Cholest-8-en-15α-ol-3-one and 5α-cholest-7-en-15α-ol-3-one were prepared in high yields from IV and V, respectively, by either selective oxidation with silver carbonate-celite or by enzymatic oxidation using cholesterol oxidase. 7α,8α-Epoxy-5α-cholestan-3β,15α-diol (VIII) was prepared in 93% yield by treatment of V with m-chloroperbenzoic acid. 5α-Cholest-8(14)-en-7α-ol-3,15-dione (IX) was prepared in 56% yield by oxidation of VIII with pyridinium chlorochromate followed by treatment of the crude product with acid. Compound IX was also obtained in 72% yield by selective chemical oxidation of 5α-cholest-8(14)-en-3β,7α,15α-triol. 5α-Cholesta-6,8(14)-dien-3,15-dione (X) was prepared in 89% yield by treatment of IX with p-toluenesulfonic acid under controlled conditions. Reduction of X with lithium tri-tert-butoxyaluminum hydride under controlled conditions gave 5α-cholesta-6,8(14)-dien-3β-ol-15-one in 84% yield.