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.     

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.     

New triterpenoids from the leaves of Abrus precatorius

Three new (1-3) triterpenoids and one known (4) triterpenoid were isolated from an acid hydrolyzed methanol-soluble extract of the leaves of Abrus precatorius. Their structures were identified as (20S,22S)-3beta,22-dihydroxycucurbita-5(10),24-diene-26,29-dioic acid delta-lactone (1), 3-O-[6'-methyl-beta-D-glucuronopyranosyl]-3beta,22beta-dihydroxyolean-12-en-29-oic acid methyl ester (2), 3-O-beta-D-glucuronopyranosylsophoradiol methyl ester (3), and sophoradiol (4) by spectroscopic techniques including 2D NMR.     

Phenolic constituents from the rhizomes of Gastrodia elata

Gastrodia elata Bl. (Orchidaceae) is an important traditional medicinal plant as well as a famous foodstuff in China. In the present article, the HPLC chromatograms of different preparation processes were reported, and structures of nine phenolic compounds, isolated from Gastrodia elata, were assigned. The isolated compounds were identified as 1,3-bis(4-hydroxybenzyl)citrate (1), gastrodin (2), 4-hydroxybenzyl alcohol (3), 1-(4-beta-D-glucopyranosyloxybenzyl)citrate (4), 4-hydroxybenzaldehyde (5), parishin B (6), 4-hydroxybenzyl methyl ether (7), 4-hydroxybenzyl ethyl ether (8), and 4-(4'-hydroxybenzyl)phenol (9). Compounds 1 and 4, named as parishin D and E, were new. Their structures were elucidated on the basis of spectral analyses, including 2D NMR spectroscopy.     

Four new aromatic allenic ethers from the fungus Xylaria sp. No. 2508

Four new aromatic allenic ethers, (7E)-3-(4-buta-2,3-dienyloxy-3-methoxy-phenyl)-acrylic acid methyl ester (1), (7E)-3-[4-(4-buta-2,3-dienyloxy-benzyloxy)-phenyl]-acrylic acid methyl ester (2), 4-(4-buta-2,3-dienyloxy-benzyloxy)-benzoic acid methyl ester (3), (7E)-3-[4-(4-buta-2,3- dienyloxy-benzyloxy)-3-methoxy-phenyl]-acrylic acid methyl ester (4) were isolated from the fungus Xylaria sp. No. 2508. The structures of those compounds were determined by analysis of spectroscopic data, mainly 2D NMR experiments.     

D:C-friedooleanane-type triterpenoids from Lagenaria siceraria and their cytotoxic activity

Four new D:C-friedooleanane-type triterpenes, 3 beta-O-(E)-feruloyl-D:C-friedooleana-7,9(11)-dien-29-ol (1), 3 beta-O-(E)-coumaroyl-D:C-friedooleana-7,9(11)-dien-29-ol (2), 3 beta-O-(E)-coumaroyl-D:C-friedooleana-7,9(11)-dien-29-oic acid (3), and methyl 2 beta,3 beta-dihydroxy-D:C-friedoolean-8-en-29-oate (6), together with five known triterpenes with the same skeleton, 3-epikarounidiol (4), 3-oxo-D:C-friedoolena-7,9(11)-dien-29-oic acid (5), bryonolol (7), bryononic acid (8), and 20-epibryonolic acid (9), were isolated from the methanol extract of the stems of Lagenaria siceraria. The structures of those compounds were elucidated using spectroscopic methods. Compounds 3 and 9 showed significant cytotoxic activity against the SK-Hep 1 cell line with IC50 values of 4.8 and 2.1 microg/ml, respectively. Based on these initially promising results, the two D:C-friedooleanane triterpenes merit further study as potential anticancer agents.     

Polysubstituted piperidines via iodolactonization: application to the asymmetric synthesis of (+)-pseudodistomin D

Conjugate addition of lithium (S)-N-allyl-N-(α-methyl-p-methoxybenzyl)amide to methyl (E,E)-hepta-2,5-dienoate furnished the corresponding β-amino ester. N-Protecting group manipulation, ring-closing metathesis, and ester hydrolysis gave enantiopure [N(1')-tert-butoxycarbonyl-1,2,3,6-tetrahydropyridin-2'-yl]ethanoic acid. Subsequent iodolactonization gave a bicyclic iodolactone scaffold. This key intermediate was elaborated to (+)-pseudodistomin D [in >99% ee and 7% yield over 16 steps from methyl (E,E)-hepta-2,5-dienoate].     

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.     

Solvent- and temperature-controlled in situ ligand reactions mediated by Cu(II) and 3'-[(E)-{[(1S,2S)-2-aminocyclohexyl]imino}methyl]-4'-hydroxy-4-biphenylcarboxlic acid

Three new compounds, CuL, CuL', and Cu(2)O(2)L'(2) (H(2)L = 3'-[(E)-{[(1S,2S)-2-aminocyclohexyl]imino}methyl]-4'-hydroxy-4-biphenylcarboxlic acid, H(2)L' = 3'-[(E)-{[(1S,2S)-2-aminocyclohexyl]imino}methyl]-4'-hydroxy-5'-nitro-4-biphenylcarboxlic acid, H(2)L' = 3'-(N,N-dimethylamino methyl)-4'-hydroxy-4-biphenylcarboxlic acid), were selectively synthesized through a controlled in situ ligand reaction system mediated by copper(II) nitrate and H(2)L. Selective nitration was achieved by using different solvent mixtures under relatively mild conditions, and an interesting and economical reductive amination system in DMF/EtOH/H(2) O was also found. All crystal structures were determined by single-crystal X-ray diffraction analysis. Both CuL and CuL' display chiral 1D chain structures, whereas Cu(2)O(2)L'(2) possesses a structure with 13×16?? channels and a free volume of 41.4?%. The possible mechanisms involved in this in situ ligand-controlled reaction system are discussed in detail.     

Isolation and biological activity of new and known isolation and biological activity of new and known diterpenoids from Sideritis stricta Boiss. & Heldr

Nine known and one new ent-kaurene diterpenoid were isolated from the acetone extract of Sideritis stricta Boiss & Heldr. The new compound, identified as ent-1 beta-hydroxy-7 alpha-acetyl-15 beta,16 beta-epoxykaurane (1) by IR, 1D and 2D NMR techniques and mass spectra, was isolated along with sideroxol (2), 7-acetyl sideroxol (3), 7-epicandicandiol (4), linearol (5), ent-7 alpha,15 beta,18-trihydroxy-kaur-16-ene (6), ent-7 alpha-acetyl,15,18-dihydroxy-kaur-16-ene (7), foliol (8), sideridiol (9) and siderol (10). The antibacterial and antifungal activities of these compounds and the whole crude acetone extract were evaluated against E. coli, S. aureus, K. pneumeonia and C. albicans.     

(1)H and (13)C NMR signal assignments of paecilin A and B, two new chromone derivatives from mangrove endophytic fungus Paecilomyces sp. (tree 1-7)

Two new natural products, named paecilin A (1) and B (2), together with two known compounds secalonic acid D (3) and (11)-cytochalasa-6(12),13-diene-1,21-dione-16,18-dimethyl-7-hydroxy-10-phenyl-(7S*,13E,16S*,18S*) (4), were isolated from the mangrove endophytic fungus, Paecilomyces sp. (tree 1-7) from the South China Sea. 1D and 2D NMR experiments including COSY, HMQC, and HMBC were used for the determination of their structures. In our cytotoxicity assays, secalonic D (3) showed cytotoxicity toward KB cells with IC(50) < 1 microg ml(-1) and inhibiting human topoisomerase I with IC(50) at 0.16 micromol ml(-1). 1, 2, and 4 showed no activity to KB cells.     

Furostanol saponins from the fresh rhizomes of Polygonatum kingianum

Ten furostanol saponins were isolated as five pairs of 25R and 25S epimers from the fresh rhizomes of Polygonatum kingianum. Seven of them were identified as new compounds, (25S)-kingianoside D (2), (25S)-kingiano-side C (4), (25R,22)-hydroxylwattinoside C (5), kingianoside E (7), (25S)-kingianoside E (8), kingianoside F (9) and (25S)-kingianoside F (10), together with three known saponins, kingianoside C (1), kingianoside D (3), and 22-hydroxylwattinoside C (6). The structures of the new saponins were determinded by detailed analysis of their 1D and 2D NMR spectra, and by comparison of the spectral data with those reported.     

The reaction of (4R,5R)- and (4S,5S)-4,5-epoxy-2(E)-hexenoates and secondary amines.

A reaction of methyl (4R,5R)-4,5-epoxy-2(E)-hexenoate 1 with N-benzylmethylamine gave a diastereomerically pure methyl (4R,5R)-4,5-epoxy-(3S)-N-benzylmethylamino hexanoate 6 and methyl (4S,5R)-4-N-benzyl-methylamino-5-hydroxy-2(E)-hexenoate 7. The former was chemoenzymatically converted to (-)-osmundalactone 11, which is an aglycone of osmundalin. On the other hand, the directly conjugated addition of dimethylamine to methyl (4S,5S)-4,5-epoxy-2(E)-hexenoate 1 followed by treatment with MeOH at 40 degrees C exclusively provided methyl (4R,5S)-4-dimethylamino-5-hydroxy-2(E)-hexenoate 16, which was converted into L-(-)-forosamine 18.     

Three antibacterial naphthoquinone analogues from cultured mycobiont of lichen Astrothelium sp.

<正>A new naphthoquinone compound named 7-hydroxyl-8-methoxyltrypethelone 3 together with two known compounds trypethelone 1 and trypethelone methyl ether 2 was isolated from cultured mycobiont of Astrothelium sp.The structures were elucidated by 1D and 2D NMR spectroscopic analysis as well as comparison with those reported in literatures.Compound 1 displayed significant antibacterial activity against Bacillus subtilis(ATCC 6633),and showed modest antibacterial activity against Staphylococcus aureus col(MRSA)(CGMCC 1.2465),while compounds 2 and 3 showed modest antibacterial activity against Enterococcus faecalis 850E(CGMCC 1.2135) and S.aureus col(MRSA)(CGMCC 1.2465).     

Two New Abietane Diterpenoids from the Roots of Tripterygium wilfordii Hook. f.

Two new abietane‐type diterpenoids, named triptobenzene R ( 1 ) and triptobenzene S ( 2 ), together with three known abietane‐type diterpenoids, triptophenolide ( 3 ), triptonodiol ( 4 ), and triptonoterpene methyl ether ( 5 ), were isolated from the roots of Tripterygium wilfordii Hook . f. Their structures and relative configurations were established by detailed spectral studies, including 1D‐ and 2D‐NMR (HSQC, HMBC, and NOESY), and HR‐ESI‐TOF‐MS, and by comparison with published data. Their absolute configurations were assigned by the CD technique, applied for the first time to abietane diterpenes from Tripterygium wilfordii. Compound 2 is the first abietane‐type norditerpenoid isolated from the genus Tripterygium.     

Monoterpene glycosides from Indigofera hetrantha

Monoterpene glycosides have been isolated from the ethyl acetate soluble fraction of Indigofera hetrantha and their structures assigned to be 3,7-dimethyl-2(E),6-octadien-5-one-1-O-beta-D-6-O-acetylglucopyranoside (1) and 3,7-dimethyl-2(E), 6-octadien-5-one-1-O-[-beta-D-6'-O-acetylglucopyra-nosyl (1' --> 6')-beta-D-glucopyranoside] (2), on the basis of spectroscopic analysis including 1D and 2D NMR techniques. Compounds 1 and 2 displayed moderate inhibitory potential against the enzyme lipoxygenase.     

Total synthesis of plakortide E and biomimetic synthesis of plakortone B

The total synthesis of plakortide E (1a) is reported. A novel palladium-catalyzed approach towards 1,2-dioxolanes as well as an alternative substrate-controlled route leading exclusively to cis-highly substituted 1,2-dioxolanes have been developed. A lipase-catalyzed kinetic resolution was employed to provide optically pure 1,2-dioxolane central cores. Coupling of the central cores and side chains was achieved by a modified Negishi reaction. All four isomeric structures of plakortide E methyl ester, namely, 26a-d were synthesized. One of the structures, 26d, was shown to be identical with the natural plakortide E methyl ester on the basis of (1)H, (13)C NMR spectra and specific rotation comparisons. With the plakortide E methyl ester (4S,6R,10R)-(-)-cis-26d and its other three isomers in hand, we successfully converted them into (3S,4S,6R,10R)-plakortone B (2a), and its isomers ent-2a, 2b and ent-2b via an intramolecular oxa-Michael addition/lactonization cascade reaction. Finally, saponification converted 1,2-dioxolane 26d into plakortide E (1a) whose absolute configuration (4S,6R,10R) was confirmed by comparison of spectral and physical data with those reported.     

Five new sesquiterpenoids and a new diterpenoid from Erigeron annuus (L.) PERS., Erigeron philadelphicus L. and Erigeron sumatrensis RETZ

The aerial parts of Erigeron annuus (L.) PERS., E. philadelphicus L. and E. sumatrensis RETZ. (Compositae) have been investigated chemically. A new sesquiterpenoid, 6beta,14-epoxyeudesm-4(15)-en-1beta-ol (1), and a new diterpenoid, philadelphinone (6), have been isolated from E. philadelphicus. Four new sesquiterpenoids, (7R*)-opposit-4(15)-ene-1beta,7-diol (2), 11-methoxyopposit-4(15)-en-1beta-ol (3), 15-methoxyisodauc-3-ene-1beta,5alpha-diol (4) and 10alpha-hydroxycadin-4-en-15-al (5), have been isolated from E. annuus. Compounds 2 and 4 were also isolated from E. sumatrensis. The structures of the new compounds were elucidated on the basis of their spectral data.     

Benzofurans and sterol from the seeds of <Emphasis Type="Italic">styrax obassia</Emphasis>

Two benzofurans (1, 2) along with five known compounds (3.7) were isolated from the seeds of S. obassia. Their structures were elucidated as methyl 3-[7-methoxy-2-(3′,4′-methylenedioxyphenyl)-5-benzofuranyl]-propionate (1), methyl 3-[2-(3′,4′-methylenedioxyphenyl)-5-benzofuranyl]-propionate (2), egonol (3), egonolacetate (4), egonol-2-methylbutanoate (5), 7-demethoxyegonol-2-methylbutanoate (6), and stigmasterol (7) on the basis of their comprehensive spectroscopic analysis including 2D NMR data. Compounds 1, 2 are obtained for the first time from nature, while this is the first record of compound 7 from the Styrax species. Published in Khimiya Prirodnykh Soedinenii, No. 4, pp. 350-353, July-August, 2008. Original article submitted May 4, 2007.     

Three cycloartane glycosides from Cimicifuga rhizome and their immunosuppressive activities in mouse allogeneic mixed lymphocyte reaction

One known (1) and two new cycloartane triglycosides, 20S,22R,23S,24R-16beta,23;22,25-diepoxy-cycloartane-3beta,23,24-triol 3-O-beta-D-glucopyranosyl-(1-->2)-beta-D-glucopyranosyl-(1-->2)-beta-D-xylopyranoside (2) and 20S,22R,23S,24R-16beta,23;22,25-diepoxy-cycloartane-3beta,23,24-triol 3-O-(6-O-trans-isoferuloyl-beta-D-glucopyranosyl)-(1-->2)-beta-D-glucopyranosyl-(1-->2)-beta-D-xylopyranoside (3), were isolated from a commercial Cimicifuga Rhizome. Their structures were determined by two dimensional (2D) NMR spectroscopic analysis and chemical evidence. These compounds suppressed the proliferation of lymphocytes in mouse allogeneic mixed lymphocyte reaction.