Noroleanane saponins from Celmisia petriei

Two biologically active noroleanane saponins from Celmisia petriei are identified as 3-O-(α-l-arabinopyranosyl (1 → 6)-β-d-glucopyranosyl (1 → 2)-α-l-arabinopyranosyl), 2β,17,23-trihydroxy-28-norolean-12-en-16-one and its 2″-O-acetyl derivative. ¹³C NMR and T₁ measurements allowed the determination of the sugar sequence and the majority of the linkage positions, but gave ambiguous results for the inner arabinose sugar. The structure of camellenodiol is revised to 3β,17-dihydroxy-28-norolean-12-en-16-one.     

Triterpenoids of Akebia quinata callus tissue

From tissue culture of Akebia quinata, three new triterpenes were isolated together with two known triterpenes, oleanolic acid and mesembryanthemoidgenic acid. The new triterpenes were characterized by spectroscopic means as 3β-hydroxy-30-norolean-12,20(29)-dien-28-oic acid, 3-epi-30-norolean-12,20(29)-dien-28-oic acid and 3β-hydroxy-29(or 30)-al-olean-12-en-28-oic acid.     

Camellidins,Antifungal Saponins Isolated from Camellia japonica

Two triterpenoid saponins were isolated from an aqueous or a methanolic extract of camellia (Camellia japonica) leaf. They had an antifungal activity characterized by abnormal germination of conidia. These saponins were composed of 3βhydroxy-18β-acetoxy-28-norolean-12-en-16-one or 3β, 8β-dihydroxy-28-norolean-12-en-16-one as aglycon, and d-glucuronic acid, dglucose and two moles of dgalactose as the sugar moiety. The authors have named these new saponins “Camellidin,” which might have value for studies in the fields of phytopathology and biochemistry.     

Sapogenins from Guaiacum officinale

Acid hydrolysis of the saponins from the stem bark of Guaiacum officinale yielded the new sapogenin 3β,20η-dihydroxy-30-norolean-12-en-28-oic acid and the artifacts 3β-hydroxy-30-norolean-12,19-dien-28-oic acid and its methyl ester. Larreagenin, sitosterol and oleanolic acid were also isolated.     

The potential of Cyathus africanus for transformation of terpene substrates

The insecticidal sesquiterpenes cadina-4,10(15)-dien-3-one and aromadendr-1(10)-en-9-one were administered to the fungus Cyathus africanus ATCC 35853. Biotransformation of the former produced (4R)-9α-hydroxycadin-10(15)-en-3-one, while the latter gave 2β-hydroxyaromadendr-1(10)-en-9-one, 2α-hydroxyaromadendr-1(10)-en-9-one and 10α-hydroxy-1β,2β-epoxyaromadendran-9-one. The bioconversion of santonin led to the production of two analogues, 11,13-dihydroxysantonin and the hitherto unreported 8α,13-dihydroxysantonin, while cedrol yielded 3β,8β-dihydroxycedrane and 3α,8β-dihydroxycedrane. Stemod-12-ene, a diterpene, was transformed to 2-oxostemar-13-ene, a hitherto unknown analogue with a rearranged carbon framework. When methyl betulonate, a triterpenoid belonging to the lupane family, was supplied to the fungus 18α-ursane and 18α-oleanane derivatives, namely 19β-hydroxy-3-oxo-18α-oleanan-28-oic acid and 19α-hydroxy-3-oxo-18α-ursan-28-oic acids, were generated. There are no previous reports of fungal transformation of a triterpene in which a skeletal rearrangement occurred. All substrate administration experiments were done in the presence of the terpene cyclase inhibitor chlorocholine chloride (CCC), using the single phase – pulse feed method.     

Lagerenyl acetate and lagerenol two tetracyclic triterpenoids with the cycloartane skeleton from Lagerstroemia lancasteri

Lagerenyl acetate and lagerenol two new tetracyclic triterpenoids with the cycloartane skeleton together with four other triterpenoids 2α-hydroxy- 3β-E-p-coumaryloxy-urs-12-en-28-oic acid (jacoumaric acid, isolated as its monoacetylmethylcarboxylate derivative), 2α-hydroxyursolic acid (isolated as its diacetate), germanicyl acetate and friedelin, and sitosterol were isolated from the leaves and twigs of Lagerstroemia lancasteri. The structures of lagerenyl acetate and lagerenol were established as 3β-acetoxycycloart-24-one and 3β-hydroxycycloart-24-one, respectively, on the basis of spectral and chemical evidence.     

Triterpenoid saponins and phenylethanoid glycosides from stem of Akebia trifoliata var. australis

A detailed phytochemical study on the 70% aqueous ethanol extract of stems of Akebia trifoliata (Thunb.) Koidz. var. australis (Diels) Rehd led to isolation of five compounds, together with 12 known triterpenoid saponins and three known phenylethanoid glycosides. The structures of the five compounds were elucidated on the basis of analysis of spectroscopic data and physicochemical properties as: 2alpha, 3beta, 23-trihydroxy-30-norolean-12-en-28-oic acid beta-D-glucopyranosyl ester (1), 2alpha, 3beta, 23-trihydroxy-30-norolean-12-en-28-oic acid beta-D-xylopyranosyl-(1-->3)-O-alpha-D-rhamnopyranosyl-(1-->4)-O-beta-D-glucopyranosyl-(1-->6)-O-beta-D-glucopyranosyl ester (2), 2alpha, 3beta, 23-trihydroxyurs-12-en-28-oic acid beta-D-xylopyranosyl-(1-->3)-O-alpha-L-rhamnopyranosyl-(1-->4)-O-beta-D-glucopyranosyl-(1-->6)-O-beta-D-glucopyranosyl ester (3), 3-beta-[(beta-D-glucopyranosyl-(1-->3)-O-alpha-L-arabinopyranosyl)oxy]-23-hydroxy-30-norolean-12-en-28-oic acid alpha-L-rhamnopyranosyl-(1-->4)-O-beta-D-glucopyranosyl-(1-->6)-O-beta-D-glucopyranosyl ester (4) and 3-beta-[(alpha-L-xylopyranosyl-(1-->2)-O-alpha-L-arabinopyranosyl)oxy]-30-norolean-12-en-28-oic acid alpha-L-rhamnopyranosyl-(1-->4)-O-beta-D-glucopyranosyl-(1-->6)-O-beta-D-glucopyranosyl ester (5), named mutongsaponin A, B, C, D and E, respectively.     

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.     

Δ5-7-Ketosterols with modified side chain: The synthesis and the effects on viability and cholesterol biosynthesis in Hep G2 cells

(22E)-3β-Hydroxysitosta-5,22-dien-7-one, (22R,23R)-3β,22,23-trihydroxysitost-5-en-7-one, and (22R,23R)-3β-hydroxy-22,23-isopropylidenedioxysitost-5-en-7-one were synthesized. The cytotoxicity and effects on cholesterol biosynthesis of the resulting 7-ketosterols, 7-ketocholesterol, and (22S,23S)-3β-hydroxy-22,23-oxidositost-5-en-7-one were studied in hepatoblastoma Hep G2 cells.     

Neo-clerodane diterpenoids from Teucrium pyrenaicum

From the aerial part of Teucrium pyrenaicum three new neo-clerodane diterpenoids have been isolated. Their structures, 3β-acetoxy-4α,18:12S,2OS: 15,16:19, 2OS-tetraepoxy-neo-cleroda-13(16),14-dien-6-one (teupyrenone), 3β,6α,19-triacetoxy- 4α,18:15,16-diepoxy-neo-cleroda-13(16),14-dien-20,12S-olide (teupyreinin), and 3β, 6α,19,2OS-tetra-acetoxy-4α,18:12S,2OS: 15,16-triepoxy-neo-cleroda-13(16), 14-diene (teupyreinidin), were established mainly by spectroscopic means.     

Diterpenoids from galeopsis angustifolia

The structures of two new diterpenoids, galeopsin and pregaleopsin, isolated from aerial parts of Galeopsis angustifolia (Labiatae) have been shown to be 8β-acetoxy-15,16-epoxy-9α-hydroxylabda-13(16),14-dien-7-one and 8β-acetoxy-9α,13R; 15,16-diepoxylabd-14-en-7-one, respectively, by chemical and spectroscopic studies. The previously known diterpenoid hispanolone (15,16-epoxy-9α-hydroxy-8α-labda-13(16),14-dien-7-one) has been also obtained from the same source. A thermal retroaldol reaction in the absence of solvent experienced by these 9-hydroxy-7-keto-labdanes is also described.     

Chromones from the tubers of Eranthis cilicica and their antioxidant activity

Chemical studies on the constituents of Eranthis cilicica led to isolation of ten chromone derivatives, two of which were previously known. Comprehensive spectroscopic analysis, including extensive 1D and 2D NMR data, and the results of enzymatic hydrolysis allowed the chemical structures of the compounds to be assigned as 8,11-dihydro-5-hydroxy-2,9-dihydroxymethyl-4H-pyrano[2,3-g][1]benzoxepin-4-one, 5,7-dihydroxy-8-[(2E)-4-hydroxy-3-methylbut-2-enyl]-2-methyl-4H-1-benzopyran-4-one, 5,7-dihydroxy-2-hydroxymethyl-8-[(2E)-4-hydroxy-3-methylbut-2-enyl]-4H-1-benzopyran-4-one, 7-[(β-d-glucopyranosyl)oxy]-5-hydroxy-8-[(2E)-4-hydroxy-3-methylbut-2-enyl]-2-methyl-4H-1-benzopyran-4-one, 7-[(β-d-glucopyranosyl)oxy]-5-hydroxy-2-hydroxymethyl-8-[(2E)-4-hydroxy-3-methylbut-2-enyl]-4H-1-benzopyran-4-one, 9-[(O-β-d-glucopyranosyl-(1→6)-β-d-glucopyranosyl)oxy]methyl-8,11-dihydro-5,9-dihydroxy-2-methyl-4H-pyrano[2,3-g][1]benzoxepin-4-one, 8,11-dihydro-5,9-dihydroxy-9-hydroxymethyl-2-methyl-4H-pyrano[2,3-g][1]benzoxepin-4-one, and 7-[(O-β-d-glucopyranosyl-(1→6)-β-d-glucopyranosyl)oxy]methyl-4-hydroxy-5H-furo[3,2-g][1]benzopyran-5-one, respectively. The isolated compounds were evaluated for their antioxidant activity.     

Synthesis of 5α-Androstane-3α,16α,17β-triol from 3β-hydroxy-5-androsten-17-one

5α-Androstane-3α, 16α 17β-triol was synthesized from 3β-hy-droxy-5-androsten-17-one. The procedure Involved catalytic hydrogenation of 3β-hydroxy-5-androsten-17-one to 3β-hydroxy-5α-androstan-17-one. This was followed by conversion of the 3β-hydroxy group to 3α-benzoyloxy group by the Mitsunobu reaction. Further treatment with isopropenyl acetate yielded 5α-androsten-16-ene-3α, 17-diol 3-benzoate 17-acetate. This was then converted to 3α, 17-dihydroxy-5α-androstan-16-one 3-benzoate 17-acetate via the unstable epoxide intermediate after treatment with $\text{m}$-cloroperoxybenzoic acid. LiAlH₄ reduction of this compound formed 5α-androstane-3α, 16α, 17β-trlol. ¹H and ¹³C NMR of various steroids are presented to confirm the structure of this compound.     

Stereochemistry of strictic acid and related furano-diterpenes from conyza japonica and grangea maderaspatana

Extraction of Conyza japonica gave strictic acid, ent-2β-hydroxy-15,16-epoxy-3,13(16),14-clerodatrien-18-oic acid and 5,7-dihydroxy-3,8,4′-trimethoxyflavone. Extraction of Grangea maderaspatana gave (-)-hardwickiic acid, ent-15,16-epoxy-1,3,13(16),14-clerodatetraen-18-oic acid and 3-hydroxy-8-acetoxypentadeca-1,9,14-trien-4,6-diyne. The structure of ent-2β-hydroxy-15,16-epoxy-3,13(16),14-cleroclatrien-18-oic acid was deduced by spectroscopic methods and by partial synthesis from (-)-hardwickiic acid and the stereochemistries of strictic acid and (ent-15,16-epoxy-1,3,13(16),14-clerodatraen-18-oic acid were established by correlation with ent-2β-hydroxy-15,16-epoxy-3,13(16),14-clerodatrien-18-oic acid.     

Metabolism of 5β-pregnane-3,20-dione and 3β-hydroxy-5β-pregnan-20-one by Digitalis suspension cultures

Digitalis purpurea normal callus suspension culture is capable of metabolizing 5β-pregnane-3,20-dione (1) to 3β-hydroxy-5β-pregnan-20-one (2), 3α-hydroxy-5β-pregnan-20-one (3), 3β-hydroxy-5β-pregnan-20-one glucoside (7) and 3α-hydroxy-5β-pregnan-20-one glucoside (8). Digitalis purpurea habituated callus suspension culture is also capable of metabolizing 1 to 2, 3, 5β-pregnane-3β,20β-diol (5), (7), (8), 5β-pregnane-3β,20α-diol monoglucoside (9) and 5β-pregnane-3α,20α-diol monoglucoside (11). Furthermore, it was observed that 3β-hydroxy-5β-pregnan-20-one (2) is converted to 7, 9 and 11 by both suspension cultures. At the same time, 1, 3, 5 and 8 were detected in normal callus, while 5β-pregnane-3β,20α-diol (4) and 5β-pregnane-3β,20β-diol monoglucoside (10) were present in the habituated callus culture.     

马尾伸筋草化学成分及抗骨质疏松活性研究

为研究马尾伸筋草(Lycopodium fargesii Hert.)的化学成分及其抗骨质疏松活性,采用硅胶、MCI、RP-18、Sephadex LH-20柱色谱及半制备高效液相色谱对马尾伸筋草的乙醇提取物进行系统分离,从乙酸乙酯部位中得到18个化合物,综合利用NMR、HR-ESI-MS等技术,分析鉴定化合物的结构,分别鉴定为α-芒柄蜡素(1)、26-去甲-8-氧化-α-芒柄蜡素(2)、serrat-14-en-3β,21α,24-triol(3)、serrat-14-en-3β,21β,24-triol(4)、1,20-eicosanediol(5)、二十三烷(6)、glycerolmonolinoleate(7)、glyceryl linolentate(8)、3-(4′-formylphenoxy)-4-methoxybenzaldehyde(9)、芹菜素(10)、对羟基苯甲醛(11)、香草酸(12)、3-羟基-4-甲氧基苯甲酸(13)、2-羟基-1-(4-羟基-3-甲氧基-苯基)-丙基-1-酮(14)、3-甲氧基-4-羟基桂皮醛(15)、8-acetoxy-5-hydroxyumbelliprenin(16)、trans-4-hydroxy-2-nonenoic acid(17)和正十烷硫醇(18)。化合物1~18均为首次从马尾伸筋草中分离得到,其中化合物16对破骨细胞活性具有显著的抑制作用,其IC₅₀为1.98μM。     

Three bridged 14β,26-epoxy-C-homo-pentacyclic triterpenes from Primula rosea

Three new bridged 14β,26-epoxy-C-homo-pentacyclic triterpenes isolated from Primula rosea have been shown to be 14β,26-epoxy-serratane-3,21-dione, 21α-hydroxy-14β,26-epoxy-serratane-3-one and 21β-hydroxy-14β,26-epoxy-serratane-3-one, respectively, on the basis of ¹H NMR, ¹³C NMR and mass spectral and chemical evidence.     

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.     

Eudesmane-type sesquiterpenes from the liverwort Apomarsupella revolute

Phytochemical investigation of the Et₂O extract of liverwort Apomarsupella revolute led to isolation and identification of five new eudesmane-type sesquiterpenoids, 6β-hydroxy-9β-acetoxy-eudesma-4,11-dien (1), 6β-hydroxy-9β-acetoxy-eudesma-4,11-dien-3-one (2), 5α,6β-dihydroxy-9β-acetoxy-eudesma-4(15),11-dien (3) 4β-hydroxy-9β-acetoxy-11,12,13-trinor-5-eudesmen-7-one (4) and 4β-methox-9β-acetoxy-11,12,13-trinor-5-eudesmen-7-one (5), two of which were trinorsesquiterpenoids. Their structures were established unequivocally on the basis of spectroscopic data analysis. All compounds were preliminary bioscreened for their cytotoxicities and antifungal activities.     

New neutral diterpenes from southern pine tall oil

Five new diterpene natural products isolated from southern pine (Pinus spp.) tall oil were characterized as 8(14),15-pimaradiene-3β,18-diol, 19-hydroxy-15,16-dinorlabd-8(17)-en-13-one, 8,13β-epoxy-14-labden-6α-ol, 8,11, 13-abietatriene-15,18-diol and 9,10-secoabieta-8,11,13-trien-18,10-olide.