Cytotoxic sterols from marine-derived fungus Pennicillium sp

A new sterol, ergosta-8(14), 22-diene-3,5,6,7-tetraol(3beta, 5alpha, 6beta, 7alpha, 22E) (1), together with four known sterols ergosta-8(9), 22-diene-3,5,6,7-tetraol (3beta, 5alpha, 6beta, 7alpha, 22E) (2), 5alpha,8alpha-epidioxy-24(S)-methylcholesta-6,22-diene-3beta-ol (3), 5alpha,8alpha-epidioxy-24(S)-methylcholesta-6,9(11), 22-triene-3beta-ol (4), 3beta,5alpha,9alpha-trihydroxyergosta-7,22-diene-6-one (5) was isolated from marine fungus Pennicillium sp. Their structures were determined based on chemical analysis and spectral methods (IR, 1D and 2D NMR, HR-FAB-MS). Compounds 1-5 were evaluated for cytotoxicity against human liver cancer cell (Hep G), and most of them exhibited potent activity. Compound 1 display the highest potency with IC50 values 10.4 microg mL-1.     

Cycloartanes, protolimonoids, a pregnane and a new ergostane from Trichilia reticulata

The new ergostane steroid ergosta-5,24(24')-diene-3beta,4beta,22R-triol (1), a pregnane, (E)-volkendusin, characterised as the diacetate (3), cycloartanes 4-6 and protolimonoids 7-9 were obtained from the leaves and twigs of Trichilia reticulata.     

New diterpene glycosides of the fungus Acremonium striatisporum isolated from a sea cucumber

Three new diterpene glycosides, virescenosides V (1), W (2), and X (3) have been isolated from a marine strain of Acremonium striatisporum KMM 4401 associated with the holothurian Eupentacta fraudatrix. Their structures have been elucidated on the basis of high resolution mass spectrometry, 1D and 2D NMR (1H, 13C, DEPT, COSY 45, COSY RCT, HSQC, HMBC, and NOESY spectra) as 19-O-beta-D-altropyranosyl-7-oxo-isopimara-8(14),15-diene-2alpha,3beta-diol (1), 19-O-beta-D-altropyranosyl-isopimara-7,15-diene-2 alpha,3 beta,6 alpha-triol (2), and 19-O-beta-D-altropyranosyl-isopimara-8,15-diene-2 alpha,3 beta,7 alpha-triol (3).     

Three new taxoids from the leaves of the Japanese yew, Taxus cuspidata

Three new taxane diterpenoids were isolated from the leaves of the Japanese yew, Taxus cuspidta. Their structures were established as 5 alpha,13 alpha-diacetoxy-taxa-4(20),11-diene-9 alpha,10 beta-diol (1), 7 beta,13 alpha-diacetoxy-5 alpha-cinnamyloxy-2(3-->20)-abeo-taxa-4(20),11-diene-2 alpha,10 beta-diol (2), and 2 alpha,10 beta,13 alpha-triacetoxy-taxa-4(20),11-diene-5 alpha,7 beta,9 alpha-triol (3) respectively on the basis of 1D and 2D NMR data.     

Two new 19-oxygenated polyhydroxy steroids from the hainan soft coral Sinularia sp

Two new 19-oxygenated polyhydroxy steroids, 24-methylcholesta-5, 24(28)-diene-3 beta, 7 beta, 19-triol-19-monoacetate (1), 24-methylcholesta-5, 24(28)-diene-3 beta, 7 beta, 19-triol-7 beta, 19-diacetate (3), together with a known steroid, 24-methylcholesta-5, 24(28)-diene-3 beta, 7 beta, 19-triol-7 beta-monoacetate (4), have been isolated from the soft coral Sinularia sp. collected from the South China Sea and characterized through interpretation of spectral data.     

Triterpenes from the spores of Ganoderma lucidum and their cytotoxicity against meth-A and LLC tumor cells

Six new highly oxygenated lanostane-type triterpenes, called ganoderic acid gamma (1), ganoderic acid delta (2), ganoderic acid epsilon (3), ganoderic acid zeta (4), ganoderic acid eta (5) and ganoderic acid theta (6), were isolated from the spores of Ganoderma lucidum, together with known ganolucidic acid D (7) and ganoderic acid C2 (8). Their structures of the new triterpenes were determined as (23S)-7beta,15alpha,23-trihydroxy-3,11-dioxolanosta-8, 24(E)-diene-26-oic acid (1), (23S)-7alpha,15alpha23-trihydroxy-3,11-dioxolanosta-8, 24(E)-diene-26-oic acid (2), (23S)-3beta3,7beta, 23-trihydroxy-11,15-dioxolanosta-8,24(E)-diene-26-oic acid (3), (23S)-3beta,23-dihydroxy-7,11,15-trioxolanosta-8, 24(E)-diene-26-oic acid (4), (23S)-3beta,7beta,12beta,23-tetrahydroxy-11,15-dioxolanos ta-8,24(E)-diene-26-oic acid (5) and (23S)-3beta,12beta23-trihydroxy-7,11,15-trioxolanosta-8,24(E )-diene-26-oic acid (6), respectively, by chemical and spectroscopic means, which included the determination of a chiral center in the side chain by a modification of Mosher's method. The cytotoxicity of the compounds isolated from the Ganoderma spores was carried out in vitro against Meth-A and LLC tumor cell lines.     

Compositions of royal jelly II. Organic acid glycosides and sterols of the royal jelly of honeybees (Apis mellifera)

Two organic acid glycosides (1, 2) and 16 sterols were isolated from the royal jelly of honeybees (Apis mellifera). The former two were monoglucosides of 10-hydroxy-2E-decenoic and 10-hydroxydecanoic acids. They are the first examples of glycosides isolated from royal jelly. The latter 16 were sterols mainly composed of 28 or 29 carbons. Among them, four compounds were new isofucosterol derivatives, and their structures were characterized as (24Z)-stigmasta-5,24(28)-dien-3beta-ol-7-one (3), (24Z)-stigmasta-5,24(28)-diene-3beta,7beta-diol (4), (24Z)-stigmasta-5,24(28)-diene-3beta,7alpha-diol (5), and (24Z)-stigmast-24(28)-ene-3beta,5alpha,6beta-triol (6) on the basis of various NMR spectroscopic data.     

Electron ionization mass spectral fragmentation of cholestane-3beta,4alpha,5alpha-triol and cholestane-3beta,5alpha,6alpha/beta-triol bis- and tris-trimethylsilyl derivatives

The electron ionization (EI) mass spectral fragmentation of the bis- and tris-trimethylsilyl derivatives of cholestane-3beta,4alpha,5alpha-triol, cholestane-3beta,5alpha,6beta-triol and cholestane-3beta,5alpha,6alpha-triol was investigated. The EI mass spectrum of the 3beta,4alpha-bis-trimethylsilyl derivative of cholestane-3beta,4alpha,5alpha-triol exhibits interesting fragment ions at m/z 142 and 332 resulting from the initial loss of TMSOH between the carbons 2 and 3 and subsequent retro-Diels-Alder (RDA) cleavage of the ring A. Trimethylsilyl transfer between the 4alpha- and the 5alpha-hydroxy groups acts significantly before RDA cleavage affording an ion at m/z 404. Complete silylation of cholestane-3beta,4alpha,5alpha-triol strongly stabilizes the molecule, affording an abundant molecular ion at m/z 636 and decreasing the abundance of the RDA cleavage. Loss of water (from the non-silylated 5alpha-hydroxy group) plays a very important role during the decomposition of the molecular ion of 3beta,6alpha/beta-bis-trimethylsilyl derivatives of cholestane-3beta,5alpha,6alpha/beta-triols. These derivatives appear to be very useful in assigning the configuration of the carbon 6. This assignment is based on the abundance of the fragment ions at m/z 321, 367 and 403, which are more prominent in the EI mass spectrum of the beta-isomer. In contrast, EI mass spectra of the tris-trimethylsilyl derivatives of cholestane-3beta,5alpha,6beta-triol and cholestane-3beta,5alpha,6alpha-triol differ only slightly and appear to be poorly informative.     

Complete 1H and 13C NMR assignments of three new polyhydroxylated sterols from the South China Sea gorgonian Subergorgia suberosa

Three new polyhydroxylated sterols, 3beta,6alpha,11,20beta,24-pentahydroxy- 9,11-seco-5alpha-24-ethylcholest-7,28-diene-9-one (1), 3-(1',2'-ethandiol)-24- methylcholest-8(9),22E-diene-3beta,5alpha,6alpha,7alpha,11alpha-pentaol (2), 24-methylcholest-7,22 E-diene-3beta,5alpha,6beta,25-tetraol (3) together with five known sterols, were isolated from the EtOH/CH2Cl2 extract of the South China Sea gorgonian Subergorgia suberosa. The complete assignments of the 1H and 13C NMR chemical shifts for these new compounds were achieved by means of 1D and 2D NMR techniques, including HSQC, HMBC, 1H--1H COSY, and NOESY spectra.     

A new geranylated aromatic compound from the mushroom Hericium erinaceum

A new geranylated aromatic compound, 5-[(2'E)-3',7'-dimethyl-2',6'-octadienyl]-4-hydroxy-6-methoxy-1-isoindolinone (1), was isolated from the fruiting bodies of the mushroom Hericium erinaceum (Bull.: Fr.) Pers. (Hericiaceae) together with three known sterols, 5alpha,6alpha-epoxy-(22E)-ergosta-8(14),22-diene-3beta,7alpha-diol (2), (22E)-ergosta-7,9(11),22-triene-3beta,5alpha,6beta-triol (3) and (22E)-ergosta-7,22-diene-3beta,5alpha,6alpha,9alpha-tetrol (4). The structure of the new compound was elucidated on the basis of spectral data.     

A new pyrrolidine derivative and steroids from an algicolous Gibberella zeae strain

A new pyrrolidine derivative, 3-hydroxy-5-(hydroxymethyl)-4-(4'-hydroxyphenoxy)pyrrolidin-2-one (1), and eight known steroids, (22E,24R)-7beta,8beta-epoxy-3beta,5alpha,9alpha-trihydroxyergosta-22-en-6-one (2, a reassigned structure of (22E,24R)-5alpha,6alpha-epoxy-3beta,8beta,14alpha-trihydroxyergosta-22-en-7-one), (22E,24R)-3beta,5alpha,9alpha-trihydroxyergosta-7,22-dien-6-one (3), (22E,24R)-3beta,5alpha-dihydroxyergosta-7,22-dien-6-one (4), (22E,24R)-ergosta-7,22-dien-3beta/,5alpha,6beta-triol (5), (22E,24R)-ergosta-5,22-dien-3beta-ol (6), (22E,24R)-5alpha,8alpha-epidioxyergosta-6,22-dien-3beta-ol (7), (22E,24R)-5alpha,8alpha-epidioxyergosta-6,9(11),22-trien-3beta-ol (8), and (22E,24R)-1(10 --> 6)-abeo-ergosta-5,7,9,22-tetraen-3alpha-ol (9), were isolated from the cultures of Gibberella zeae, an endophytic fungus isolated from the marine green alga Codium fragile. Their structures and relative stereochemistry were elucidated by 1D, 2D NMR and mass spectroscopic techniques. Compound 1 showed cytotoxicity against A-549 and BEL-7402 cell lines.     

Synthesis of steroid 24,20-lactones by means of phenylselenolactonization

A synthesis of (20 R)- and (20 S)-3β-methoxy-5-cholen-24,20-lactones (7a and 7b) from 3β-methoxy-5-androsten-17-one (2) is described. The 17-ketone 2 was treated with isopropenyllithium to give 3β-methoxy-17α-(prop-l'-en-2'-ylo)-5-androsten-17β-ol (3). Compound 3 on reaction with ethyl orthoacetate and Claisen rearrangement of intermediate 17β-orthoester furnished ethyl esters of (E)- and (Z)-3β-methoxy-chol-5,17(20)-diene-24-acids (4b and 4a). Hydrolysis of ester groups in 4a and 4b and phenylselenolactonization afforded stereospecifically and regioselectively unsaturated (20 R)- and (20 S)-3β-methoxy-chol-5,16-diene-24, 20-lactones(6a and 6b), respectively. Reduction of double bond 16-17 in 6a and 6b gave the final products 7a and 7b. The phenylselenolactonization of(E)- and (Z)-3β-methoxy-chol-5,17(20)-diene-24-acids (5b and 5a) and spontaneous elimination of phenylselenyl moiety was investigated and compared with iodolactonization of the same unsaturated acids.     

Cucurbitane triterpenoids from Momordica charantia

Three new cucurbitane-type triterpenoid saponins, 23-O-beta-D-allopyranosyl-5beta,19-epoxycucurbita-6,24-diene-3beta,22(S),23(S)-triol-3-O-beta-D-glucopyranoside (1), 23-O-beta-D-allopyranosyl-5beta,19-epoxycucurbita-6,24-diene-3beta,22(S),23(S)-triol-3-O-beta-D-allopyranoside (2), and 23-O-beta-D-allopyranosyl-5beta,19-epoxycucurbita-6,24-diene-3beta,19(R), 22(S),23(S)-tetraol-3-O-beta-D-allopyranoside (3), named momordicoside M, N, and O, respectively, along with one known saponin momordicoside L (4), were isolated from the fresh fruits of Momordica charantia. The structures of these saponins were elucidated on the basis of chemical properties and spectral data.     

小刺豆荚软珊瑚甾醇类化合物的提取、分离及鉴定

从西沙群岛海区采集的小刺豆荚软珊瑚（Lobophytummicrospiculatum）中,通过乙醇提取、乙酸乙酯-水分配、硅胶色谱分离和GC／MS分析等方法,分离、鉴定出11种甾醇。其中柳珊瑚甾醇（11）的质量分数占65.6％。22,24-二甲基-胆甾-5,22（23）-二烯-3β-醇（4）是首次从自然界发现的新化合物,它的发现为柳珊瑚甾醇的生源假说提供了进一步佐证。     

Microbial hydroxylation of pregnenolone derivatives

Pregnenolone and pregnenolone acetate were incubated with the fungi Cunninghamella elegans, Rhizopus stolonifer and Gibberella fujikuroi. Incubation of with C. elegans yielded metabolites, 3beta,7beta,11alpha-trihydroxypreg-5-en-20-one, 3beta,6alpha,11alpha,12beta,15beta-pentahydroxypreg-4-en-20-one and 3beta,6beta,11alpha-trihydroxypreg-4-en-20-one, while incubation with G. fujikuroi yielded two known metabolites, 3beta,7beta-dihydroxypregn-5-en-20-one and 6beta,15beta-dihydroxypreg-4-ene-3,20-dione. Metabolites and were found to be new. Fermentation of by C. elegans yielded four known oxidative metabolites, androsta-1,4-diene-3,17-dione, 6beta,15beta-dihydroxyandrost-4-ene-3,17-dione and 11alpha,15beta-dihydroxypreg-4-ene-3,20-dione. Fermentation of with R. stolonifer yielded two known metabolites, 11alpha-hydroxypreg-4-ene-3,20-dione and. Compounds were screened for their cholinesterase inhibitory activity in a mechanism-based assay.     

Structure of a new sterol from the South China sponge Dysidea fragilis

A new sterol, 5a-cholesta-8(14),24(25)-diene-3/β, 6a-diol (1) and a known sterol (24Z)-24-ethyl-cholesta-7(8),24(28)-diene-3β,5a,6β-triol (2) have been isolated from the South China Seasponge Dysidea fragilis. The structure and relative stereochemistry of 1 were established by spectralanalysis, including 2D NMR experiments.     

Six new dammarane-type triterpene saponins from the leaves of Panax ginseng

Six new minor saponins, together with known ginsenosides, were isolated from the leaves of Panax ginseng. The new saponins were named as ginsenoside-Rh5, -Rh6, -Rh7 -Rh8, -Rh9 and -Rg7, and their structures were elucidated on the basis of chemical and physicochemical evidence to be as follows: ginsenoside-Rh5: 3beta,6alpha,12beta,24zeta-tetrahydroxy-dammar-20(22),25-diene 6-O-beta-D-glucopyranoside (1), -Rh6: 3beta,6alpha12beta,20(S)-tetrahydroxy-25-hydroperoxy-dammar-23-ene 20-O-beta-D-glucopyranoside (2), -Rh7: 3beta,7beta,12beta,20(S)-tetrahydroxy-dammar-5,24-diene 20-O-beta-D-glucopyranoside (3), -Rh8: 3beta,6alpha,20(S)-trihydroxy-dammar-24-ene-12-one 20-O-beta-D-glucopyranoside (4), -Rh9: 3beta,6alpha,20(S)-trihydroxy-12beta,23-epoxy-dammar-24-ene 20-O-beta-D-glucopyranoside (5) and -Rg7: 3-O-beta-D-glucopyranosyl 3beta,12beta,20(S),24(R)-tetrahydroxy-dammar-25-ene 20-O-beta-D-glucopyranoside (6).     

Two new polyporusterones isolated from the sclerotia of Polyporus umbellatus

In the course of searching for marker components, two new polyporusterones were isolated from the sclerotia of Polyporus umbellatus, together with another three known analogs. The structures of the new ones were elucidated as (20S,22R,24R)-16,22-epoxy-3beta,14alpha,23beta,25-tetrahydroxyergost-7-en-6-one (1) and (23R,24R,25R)-23,26-epoxy-3beta,14alpha,21alpha,22alpha-tetrahydroxyergost-7-en-6-one (2) by chemical and spectroscopic means, including HR-FAB-MS, 1D- and 2D-NMR.     

New triterpene glycosides from Camptosorus sibiricus

Two new cycloartane glycosides were isolated from the whole herbs of Camptosorus sibiricus Rupr. By means of chemical and spectroscopic methods (1D and 2D NMR, HRMS, ESI-MS), the structures were established as (24R)-3beta,7beta,24,25,30-pentahydroxycycloartane-30-O-coumaroyl-3-O-beta-D-glucopyranosyl-24-O-beta-D-glucopyranosyl-(1 --> 6)-beta-D-glucopyranoside (1) and (24R)-3beta,7beta,24,25,30-pentahydroxy-1-ene-cycloartane 24-O-beta-D-glucopyranoside (2). The two new compounds were inactive in vitro against A375-S2 and Hela human tumor cell lines using the MTT method.     

Microbial transformation of dehydroepiandrosterone

Transformation of dehydroepiandrosterone (DHEA) (1) was carried out by a plant pathogen Rhizopus stolonifer, which resulted in the production of seven metabolites. These metabolites were identified as 3beta,17beta-dihydroxyanandrost-5-ene (2), 3beta,17beta-dihydroxyandrost-4ene (3), 17beta-hydroxyandrost-4-ene-3-one (4), 3beta,11-dihydroxyandrost-4-ene-17-one (5), 3beta,7alpha-dihydroandrost-5-ene-17-one (6), 3A,7alpha,17beta-trihydroxyandrost-5-ene (7) and 11beta-hydroxyandrost-4,6-diene-3,17-dione (8). The structures of the transformed products were determined by the spectroscopic techniques.