Cytotoxic diterpenoids from the roots of Euphorbia ebracteolata

Three new diterpenoids, yuexiandajisu D (1), E (2) and F were isolated from the roots of Euphorbia ebracteolata, along with eight known diterpenoids, jolkinolide B (4), jolkinolide A, ent-11alpha-hydroxyabieta-8(14),13(15)-dien-16,12alpha-olide (6), ent-(13S)-hydroxyatis-16-ene-3,14-dione, ent-3beta,(13S)-dihydroxyatis-16-en-14-one, ent-3-oxokaurane-16alpha,17-diol, ent-16alpha,17-dihydroxyatisan-3-one and ent-atisane-3beta,16alpha,17-triol. The structures of all compounds were deduced using spectroscopic methods and confirmed for 1 and 2 by single-crystal X-ray diffraction. A biogenetic pathway for the formation of 1 and 2 is proposed briefly. Cytotoxic activities were evaluated against ANA-1, B 16 and Jurkat tumor cells. Jolkinolide B (4) displayed modest activity on ANA-1, B 16 and Jurkat tumor cells with IC50 values 4.46 x 10(-2), 4.48 x 10(-2), 6.47 x 10(-2) microM, and ent-11alpha-hydroxyabieta-8(14),13(15)-dien-16,12alpha-olide (6) showed significant activity against ANA-1 and Jurkat cells with IC50 values 7.12 x 10(-3) and 1.79 x 10(-2) microM. Compound 1 was found to be slightly active against ANA-1 cells with an IC50 value 2.88 x 10(-1)microM. Structure-activity relationships of isolated compounds are also discussed.     

Three new diterpenoids from Coleus forskohlii Briq

Three new diterpenoids, forskolin G(2), forskolin H(3), forskolin I(4), were isolated from the whole plant of the Coleus forskohlii Briq., and their structures were elucidated as 1alpha,6beta-diacetoxy-8,13-epoxylabd-14-en-11-one, 1alpha-hydroxy-6beta,7beta-diacetoxy-8,13-epoxylabd-14-en-11-one, and 1alpha,9alpha-dihydroxy-6beta,7alpha-diacetoxy-8,13-epoxylabd-14-en-11-one on the basis of spectral data.     

Three new pimaren diterpenoids from marine mangrove plant, Bruguiera gymnorrhiza

Three new pimaren diterpenoids, ent-8(14)-pimarene-15R, 16-diol (1), ent-8(14)-pimarene-1alpha,15R,16-triol (2), and (5R, 9S, 10R, 13S, 15S)-ent-8(14)-pimarene-1-oxo-15R,16-diol (3), along with three known diterpenoids (4-6) have been isolated from the stem of mangrove plant Bruguiera gymnorrhiza. The structures of compounds 1-3 were determined by extensive spectroscopic (2D NMR, MS, IR, and CD) analysis, and 3 and 5 showed moderate cytotoxic activities against L-929 and K562, respectively.     

Diterpenoids from the Chinese herb Caryopteris terniflora and their antibacterial and antitumor activity

Two ent-kaurene type diterpenoids, diterpenoids A (1) and B (2) were isolated from the Chinese herb Caryopteris terniflora and defined as ent-7beta, 11alpha,14-trihydroxy-18-aldehyde-11beta-20-epoxy-kaur-16-en15-one and ent-7beta,14-dihydroxy-11alpha-methoxy-18-aldehyde-11beta-20-epoxy-kaur-16-en-15-one respectively. Compounds 1 and 2 showed significant antibacterial and antitumour activity.     

Two new diterpenoids from Coleus forskohlii

Two new diterpenoids, forskolins I and J, have been isolated in our further investigation on Coleus forskohlii (Willd.) Briq. collected in Yunnan Province. Their structures have been determined as 1alpha,6beta-diacetoxy-7beta,9alpha-dihydroxy-8,13-epoxylabd-14-en-11-one (1) and 1alpha,9alpha-dihydroxy-6beta,7beta-diacetoxy-8,13-epoxylabd-14-en-11-one (2) by spectral methods (including 1D and 2D NMR techniques).     

Three novel bicyclic taxane diterpenoids with verticillene skeleton from the needles of Chinese yew, Taxus chinensis var. mairei.

Three novel bicyclic taxane diterpenoids with the verticillene skeleton were isolated from the needles of Chinese yew, Taxus chinensis var. mairei. Their structures were established as (3E,7E)-2 alpha, 10 beta, 13 alpha, 20-tetraacetoxy-5 alpha-hydroxy-3,8-secotaxa-3,7,11-trien-9-one (1), (3E,7E)-2 alpha, 5 alpha, 10 beta, 13 alpha-tetraacetoxy-20-hydroxy-3,8-secotaxa-3,7,11-trien-9-one (2), and (3E,7E)-10 beta, 13 alpha-diacetoxy-2 alpha, 5 alpha, 20-trihydroxy-3,8-secotaxa-3,7,11-trien-9-one (3) on the basis of 1D, 2D NMR and HR-MS spectroscopic analysis. Verticillene skeleton was considered as the biogenetic intermediate of taxane diterpenoids, isolation of bicyclic taxane diterpenoids with verticillene skeleton from this plant provides direct proof for this hypothesis.     

A new rearranged abietane diterpenoid from Clerodendrum kaichianum Hsu

A new abietane diterpenoid, (3S,16R)-12,16-epoxy-3,6,11,14,17-pentahydroxy-17(15?→?16)-abeo-5,8,11,13-abietatetraen-7-one (1), was isolated from the stems of Clerodendrum kaichianum Hsu, together with four known diterpenoids. The structures of the isolated compounds were assigned on the basis of their NMR spectra including 2D NMR techniques such as COSY, HMQC, and HMBC experiments, and were compared with those of the literature data. This new compound showed significant cytotoxicity against the HL-60 and A-549 tumor cell lines.     

Taibaijaponicains C and D: two new diterpenoids from Isodon japonica

Two new C-20-oxygenated ent-kaurene diterpenoids, taibaijaponicains C and D, together with five known compounds, were isolated from the ethanol extract of the leaves and branches of Isodon japonica (Burm. f.) Hara. The structures of new compounds were elucidated as 1 alpha-aectoxy-7 beta,12 beta,15 alpha-trihydroxy-16 alpha-hydroxymethyl-7,20-epoxy- ent-kaurane and 1 alpha-acetoxy-2 beta,3 alpha,6 beta,7 beta,12 beta-pentahydroxy-7,20;19,20-diepoxy- ent-kaur-16-en-15-one, respectively, on the basis of detailed spectroscopic analysis.     

Three new diterpenoids from Coleus forskohlii Briq

Three new diterpenoids, forskolin G(2), forskolin H(3), forskolin I(4), were isolated from the whole plant of the Coleus forskohlii Briq., and their structures were elucidated as 1α,6β-diacetoxy-8,13-epoxylabd-14-en-11-one, 1α-hydroxy-6β,7β-diacetoxy-8,13-epoxylabd-14-en-11-one, and 1α,9α-dihydroxy-6β,7α-diacetoxy-8,13-epoxylabd-14-en-11-one on the basis of spectral data.     

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

Five taxane diterpenoids were isolated from the seeds of the Japanese yew, Taxus cuspidata Sieb. et Zucc. The structures were established as 2 alpha,7 beta,13 alpha-triacetoxy-5 alpha-(3'-dimethylamino-3'-phenyl)-propionyloxy-2(3-->20)-aboe+ ++-taxa-9,10-dione (1) and 2 alpha,7 beta,9 alpha,10 beta-tetraacetoxy-5 alpha-[(2R,3S),N,N-dimethyl-3-phenylisoseryloxy]-taxa-4(20),11- dien-13-one (2), 2 alpha, 9 alpha, 10 beta-triacetoxy-5 alpha-cinnamoxy-taxa-4(20),11-diene-13 alpha-ol (3), taxezopidine J (4), and taxuspine D (5) on the basis of 1D, 2D NMR, and MS spectral analysis. Compounds 1, 2, and 3 are new compounds.     

Antioxidative 7-oxodehydropodocarpane-type trinorditerpenes from the bark of Taiwania cryptomerioides

Five new 7-oxopodocarpane-type trinorditerpenes together with 1beta,13,14-trihydroxy-8,11,13-podocarpatrien-7-one ( 1) were isolated from the bark of Taiwania cryptomerioides. By using NMR and other spectral methods, the structures of five new compounds, 14-hydroxy-13-methoxy-8,11,13-podocarpatriene-3,7-dione ( 2), 1beta,14-dihydroxy-13-methoxy-8,11,13-podocarpatrien-7-one ( 3), 13,14-dihydroxy-8,11,13-podocarpatriene-3,7-dione ( 4), 3beta,13,14-trihydroxy-8,11,13-podocarpatrien-7-one ( 5), and 1beta,13,14-trihydroxy-8,11,13-podocarpatriene-2,7-dione ( 6), were elucidated. Compounds 1, 4, 5, and 6 exhibited strong antioxidative activity.     

Antimicrobial principle from Aframomum longifolius

Antimicrobial activity-directed fractionation of the seeds of Aframomum longifolius (Zingiberaceae) afforded two new labdane-type diterpenoids, 15-hydroxy-15-methoxylabda-8(17), 12( E)-dien-16-al (aframolin A) ( 1) and 8beta(17)-epoxy-15,15-dimethoxylabd-12( E)-en-16-al (aframolin B) ( 2), together with the known diterpenes labda-8(17),12( E)-diene-15,16-dial ( 3) and aframodial ( 4). Their structures were determined by spectroscopic methods. Compound 4 showed significant antimicrobial activity against Cryptococcus neoformans, Staphylococcus aureus and methicillin-resistant S. aureus (MRS) while 1, 2 and 3 were found to be inactive.     

Two new dammarane triterpene glycosides from the rhizomes of Panax notoginseng

Two new dammarane triterpene glycosides named notoginsenosides Rw 1 (1) and Rw 2 (2) were isolated from the rhizomes of Panax notoginseng, together with 20 known compounds including protopanaxadiol (3), protopanaxatriol (4), ginsenosides Rb1 (5), Rd (6), Re (7), Rg1 (8), Rg2 (9), 20-(S)-Rg3 (10), 20-(R)-Rg(3) (11), Rh1 (12), Rh4 (13), Rf (14), 20-O-glucopyranosyl Rf (15), notoginsenosides R1 (16), R2 (17), T5 (18), S (19), T (20), and Fa (21), and koryoginsenoside R1 (22). Based on FABMS, HRFABMS, IR, (1)H, 13C, and 2D-NMR (HSQC, HMBC, and COSY) spectral data, the structures of the new compounds were elucidated as 6-O-beta-d-xylopyranosyl-20-O-beta-d-xylopyranosyl-(1 --> 6)-beta-d-glucopyranosyldammar-24-ene-3beta,6alpha,12beta,20(S)tetraol (1) and 6-O-beta-d-xylopyranosyl-(1 --> 2)-beta-d-glucopyranosyldammar-22-ene-(trans)-3beta,6alpha,12beta,20(S), 25-pentaol (2). Compounds 3, 4, 13, and 22 were isolated from P. notoginseng for the first time.     

A cytotoxic butenolide,two new dolabellane diterpenoids,a chroman and a benzoquinol derivative formosan Casearia membranacea

Investigation of a cytotoxic chloroform-soluble fraction of the stem of Casearia membranacea (Flacourtiaceae) led to the isolation of five new compounds, including one butenolide, casealactone (1), one chroman, caseamemin (2), two dolabellane diterpenoids, casearimene A (3) and casearimene B (4), one benzoquinol ether, casearinone (5), together with fifteen known compounds, including two amides, N- trans-feruloyltyramine (6) and N- cis-feruloyltyramine (7), six steroids, beta-sitosterol (8), stigmast-5-ene-3beta,7alpha-diol (9), stigmast-5-ene-3beta,7beta-diol (10), stigmastane-3beta,5alpha,6beta-triol (11), beta-sitostenone (12), beta-sitosterol 3- O-beta-glucoside (13), two triterpenoids, squalene (14) and friedelin (15), one lignan, (+/-)-syringaresinol (16), two benzenoids, syringaldehyde (17) and vanillic acid (18), one ester, methyl hexadecanoate (19), and anthraquinone (20), respectively. Among these isolates, 1 showed cytotoxicity against P-388 and HT-29 cancer cell lines in vitro, and 6 and 7 showed cytotoxicity against the P-388 cancer cell line. The structures of these compounds were determined by means of spectroscopic techniques, and the structure of 3 was confirmed by X-ray crystallographic analysis.     

Anti-complement activity of norlignans and terpenes from the stem bark of Styrax japonica

A new norlignan, styraxlignolide A (1), and two new terpenes, styraxosides A (2) and B (3), were isolated from the MeOH-soluble fraction of Styrax japonica Sieb. et Zucc. (Styracaceae) stem bark, together with two known compounds, egonol (4) and masutakeside I (5). The new compounds were determined as 5-(3'-hydroxypropyl)-7-methoxy-2-(3',4'-dimethoxyphenyl)-benzofuran 3'- O-[beta-D-xylopyranoside-(1-->6)-beta- D-glucopyranoside] (1), 3beta,7beta-dihydroxy-4alpha,4beta,8beta,10beta,14alpha-pentamethyl-5alpha-gon-16-en-2-one 3-O-[beta-D-glucopyranoside-(1-->2)-beta-D-glucopyranoside] (2), and 3beta,17beta-dihydroxy-28-norolean-12-en-16-one 3-O-[alpha-L-rhamopyranoside-(1-->2)-beta-D-glucuronopyranoside] (3) by spectroscopic means including 2D-NMR. The five compounds were tested in vitro for anti-complement activity against the complement system. Compounds 1, 3, 4, and 5 displayed inhibitory activity in the anti-complement assay, with IC50 values of 123, 65, 33, and 166 microM, respectively. Compound 1a and camellenodiol (3a), obtained from acid hydrolysis of 1 and 3, respectively, did not affect the hemolytic activity of human serum against sensitized erythrocytes. This shows that a sugar seems to play a role of enhancing significantly anti-complement activity.     

Lignan and terpene constituents from the aerial parts of saussurea pulchella

Chromatographic separation of the MeOH extract from the aerial parts of Saussurea pulchella led to the isolation of seven terpenes (1-4, 11-13), and eight phenolics (5-10, 14-15). Their structures were determined by spectroscopic means to be (3S)-3-O-(3',4'-diangeloyl-beta-D-glucopyranosyloxy)-3,7-trimethylocta-1,6-diene (1), 7delta-methoxy- 4(14)- oppositen-1beta-ol (2) 4(15)- eudesmene-1beta, 6alpha-diol (3), 3alpha-hydroxy-5, 6-epoxy-7-megastigmen-9-one (4), (+)-syringaresinol (5), (7S, 8R, 8'R)-5,5'-dimethoxylariciresinol (6), 8alpha-hydroxypinoresinol (7), (7'R, 8'R)-2,2'- dimethoxy-4- (3-hydroxyl-propenyl)-4'-(1,2,3-trihydroxypropyl)-biphenyl ether (8), 4-allyl-2,6- dimethoxyphenyl glucoside (9), 2-methoxy-4-(2-propenyl)phenyl beta-D-glucoside (10), (-)-oplopan-4-one- 10alpha-O-beta-D-glucoside (11), linalyl-O-beta-D-glucoside (12), amarantholidoside IV (13), (+)-1-hydroxypinoresinol 1-O-beta-D-glucoside (14), and syringin (15). Compounds 1-3 and 8-13 were first isolated from the genus Saussurea. The isolated compounds were examined for cytotoxic activity against four human cancer cell lines in vitro using the sulforhodamin B bio assay method.     

A new isopimarane-type diterpene and a new natural atisane-type diterpene from Excoecaria agallocha

From the woods of Excoecaria agallocha, a new isopimarane-type diterpene, 3alpha,11beta-dihydroxy-ent-isopimara-8(14),15-dien-2-one and a new natural atisane-type diterpene, 16beta-hydroxy-ent-atisan-3-one were isolated together with three known compounds, ribenone, ent-labda-8(17),13E-diene-3beta,15-diol, and ent-3beta-hydroxybeyer-15-ene-2,12-dione. Their structures were determined by spectral data and x-ray crystallography evidence.     

Two new bislabdane-type diterpenoids and three new diterpenoids from the roots of Cunninghamia lanceolata

Two new bislabdane-type diterpenoids lanceolatin (1), lancelatol (2) and three new diterpenoids 15-nor-14-oxo-8(17),12-labdanien-14,18-dionic acid (3), 8(17),12,14-labdantrien-18-oic acid (4) and 8(17),12,14-labdantrien-18-ol (5), together with 7 known diterpenoids were isolated from the roots of Cunninghamia lanceolata. Their structures were determined by spectroscopic and chemical methods. All of these compounds were isolated from the species for the first time. One of the isolated compounds showed a significant inhibition effect on mouse hind-paw edema induced by carrageenan.     

New sesquiterpenes from Erigeron annus

Four new and five known eudesmane-type sesquiterpenes were isolated from the aerial parts of Erigeron annus. The structures of these new compounds were elucidated by spectral means, including 2D-NMR analysis, to be 1 beta,4 beta-dihydroxyeudesman-11-ene; 1 beta,7 alpha-dihydroxyeudesman-4(15)-ene; (1 R,5 S,6 S,7 S,10 R)-1 beta, 6 alpha-dihydroxyeudesman-4-one and 1 beta- D-glucopyranosyloxy-6 alpha-hydroxyeudesman-4(15)-ene. In addition, a chemical transformation of a known compound 1 beta,6 alpha-dihydroxy-eudesman-4 (15)-ene was carried out and the derivative 1beta,6alpha-dihydroxy-4beta(15)-epoxyeudesmane was obtained. Some of the compounds were evaluated for their in vitro antitumor activities.     

Isolation, synthesis, and biological activity of five metabolites of danazol.

Metabolites of danazol (17 alpha-pregna-2,4-dien-20-yno[2,3-d]isoxazol-17-ol), an orally effective pituitary gonadotropin inhibitory agent devoid of estrogenic and progestational activites, were isolated from urine of a female subject who had taken danzol orally at a dose of 800 mg/day for 7 days, The metabolites isolated were 17-hydroxy-17alpha-pregn-4-en-20-yn-3-one (11), 17-hydroxy-2alpha-(hydroxymethyl)-17alpha-pregn-4-3n-20-yn-3-one (5), 17-hydroxy-2-(hydroxymethyl)-17alpha-pregna-1,4-dien-20-yn-3-one(7), 6beta,17-dihydroxy-2alpha-(hydroxymethyl)-17alphapregn-4-en-20-yn-3-one(8), and 6beta, 17-dihydroxy-2(hydroxymethyl)-17alphapregna-1,4-dien-20yn-3-one(10). None of these metabolites exhibited pituitary inhibiting activity comparable to danazol.