Megastigmane glucosides from Equisetum debile and E. diffusum

A new megastigmane diglucoside, (3S,5R,6S,7E,9S)-megastigman-7-ene-5,6-epoxy-3,9-diol 3,9-O-beta-D-diglucopyranoside (3), was isolated from the aerial portion of Equisetum debile along with macarangioside D (debiloside A), sammangaoside A, (6R,9S)-3-oxo-alpha-ionol 9-O-beta-D-glucopyranoside, debiloside B, kaempferol 3-O-sophoroside, kaempferol 3,7-O-beta-D-diglucopyranoside, kaempferol 3-O-sophoroside-7-O-beta-D-glucopyranoside, phenylethyl O-beta-D-glucopyranoside, (Z)-3-hexenyl O-beta-D-glucopyranoside, (7S,8R)-dehydrodiconiferyl 4-O-beta-D-glucopyranoside, and L-tryptophan. The absolute configuration at C-6 of the original structure of debilo-side A was revised to 6R-configuration, and was identical with macarangioside D (1). From the aerial portion of E. diffusum, four compounds, sammangaoside A, kaempferol 3-O-sophoroside and L-tryptophan and (3S,5R,6S,7E,9S)-megastigman-7-ene-5,6-epoxy-3,9-diol 3-O-beta-D-glucopyranoside were identified. The spectroscopic data of (3S,5R,6S,7E,9S)-megastigman-7-ene-5,6-epoxy-3,9-diol 3-O-beta-D-glucopyranoside (13) were found to be identical with corchoionoside A (9R-isomeric compound). The structure of corchoionoside A was also discussed. Structure determinations were based on physical data and spectroscopic evidence.     

Studies on Nepalese crude drugs. XXIX. Chemical constituents of Dronapuspi, the whole herb of Leucas cephalotes SPRENG

From the whole herb of Leucas cephalotes SPRENG., new labdane-, norlabdane- and abietane-type diterpenes named leucasdins A (1), B (2) and C (3), respectively, and two protostane-type triterpenes named leucastrins A (4) and B (5) were isolated, together with a known triterpene, oleanolic acid, five sterols, 7-oxositosterol, 7-oxostigmasterol, 7alpha-hydroxysitosterol, 7alpha-hydroxystigmasterol and stigmasterol, and eight flavones, 5-hydroxy-7,4'-dimethoxyflavone, pillion, gonzalitosin I, tricin, cosmosin, apigenin 7-O-beta-D-(6-O-p-coumaroyl)glucopyranoside, anisofolin A and luteolin 4'-O-beta-D-glucuronopyranoside. The structures of 1--5 were determined as (3S,6R,8R,9R,13S,16S)-9,13,15,16-bisepoxy-3,16-diacetoxy-6-formyloxylabdane, (3S,6R)-3-acetoxy-6-formyloxy-iso-ambreinolide, (4R,9S,12R,13R)-12,13-dihydroxyabiet-7-en-18-oic acid, (3S,17S,20S,24S)-3,20-dihydroxy-24-methylprotost-25-en, and (3S,17S,20S,24S)-3,20,24-trihydroxyprotost-25-en respectively, based on spectral and chemical data.     

Structural Changes and Phase Transitions in Whitlockite-Like Phosphates

New compounds with a g -Ca 3 (PO 4 ) 2 structure type were found in three systems: Sr 9+ x M 1.5 m x (PO 4 ) 7 ( M = Mn, Fe, Co, Ni, Cu, and Cd; space group R 3 m ; Z = 3), Sr 9 R (PO 4 ) 7 ( R = Al, Sc, Cr, Fe, Ga, In, and Gd-Lu; space group P 2/ c , Z = 4), and Sr 9+2 x M 1+ x A 1 m 6 x (PO 4 ) 7 ( M = Mn, Ni, Cd; space group R 3 c and Z = 6 for A = Na, K; space group P 2/ m and Z = 4 for A = Li). Crystal structures of these compounds were determined by time-of-flight neutron, synchrotron X-ray, and laboratory X-ray powder diffraction. Reversible polar-to-centrosymmetric phase transitions ( R 3 c {\begin{array}{c}\\[-14pt]\hspace*{.5pt}\to\\[-7pt]\hspace*{-.5pt}\gets \end{array}} R 3 m ) were observed at high temperatures in Ca 3 m x Sr x (PO 4 ) 2 (0 h x h 12/7), Ca 10.5 m 1.5 x Fe x (PO 4 ) 7 (0 h x h 1), and Ca 9 R (PO 4 ) 7 . Solid solutions Ca 3 m x Sr x (PO 4 ) 2 (13/7 h x h 16/7) are centosymmetric with space group R 3 m at room temperature. These phase transitions were studied by high-temperature X-ray diffraction, second-harmonic generation, DSC, electric-conductivity and dielectric measurements.     

A new neolignan glycoside from the leaves of Acer truncatum

A new neolignan glycoside, (7R,8R)-7,8-dihydro-9'-hydroxyl-3'-methoxyl- 8-hydroxymethyl-7-(4-hydroxy-3-methoxyphenyl)-1'-benzofuranpropanol 9'-O-beta-D- glucopyranoside (1) was isolated from the leaves of Acer truncatum along with (7R,8R)-7,8-dihydro-9'-hydroxyl-3'-methoxyl-8-hydroxymethyl-7-(4-O-alpha-L-rhamno- pyranosyloxy-3-methoxyphenyl)-1'-benzofuranpropanol (2), schizandriside (3), lyoniresinol (4), berchemol (5), (-)-pinoresinol-4-O-beta-D-glucopyranoside (6), hecogenin (7), chlorogenic acid (8) and neochlorogenic acid (9). Their structures were elucidated on the basis of extensive spectroscopic data. The absolute configuration of compounds 1 was established by its CD spectrum. The antibacterial activities of compounds 1-7 were evaluated.     

A Convenient Method for Synthesis of Novel Cyclic Ethers (1R,2R,3R,5S,7S,9R,12R)-3-(t-Butyldimethylsilyl)oxy-7-methoxymethyl-oxy-2,10-dimethyl-12-oxatricyclo [7.2.1.0~(5,12)] dodecane

Coloradocin, a novel macrolide antibiotic from cultures of Actinoplanes coloradoensis1exhibits activity against pathogenic anaerobic and microaerophilic species2. Because itslow toxicity and substantial oral activity3, , as well as its unusual structure5, several 4research groups initiated approaches towards the synthesis of coloradocin6, whichculminated in the synthesis of 18-deoxynargenicin A1 by Kallmerten et al.7. …     

Glycosides of Atractylodes lancea

Five sesquiterpenoid glycosides (two guaiane-type glycosides and three eudesmane-type glucosides) and a glucoside of an acetylene derivative were newly isolated from the water-soluble portion of the methanolic extract of Atractylodes lancea rhizome together with 26 known compounds. Their structures were characterized as atractyloside A 14-O-beta-D-fructofuranoside, (1S,4S,5S,7R,10S)-10,11,14-trihydroxyguai-3-one 11-O-beta-D-glucopyranoside, (5R,7R,10S)-isopterocarpolone beta-D-glucopyranoside, cis-atractyloside I, (2R,3R,5R,7R,10S)-atractyloside G 2-O-beta-D-glucopyranoside, and (2E,8E)-2,8-decadiene-4,6-diyne-1,10-diol 1-O-beta-D-glucopyranoside on the basis of chemical and spectroscopic investigation. The presence of six characteristic guaiane-type glucosides in both rhizomes of A. lancea and Atractylodes japonica suggested a close chemotaxonomic relationship between them.     

Three new megastigmane glucopyranosides from the Cardamine komarovii

Three new megastigmane glucopyranosides, komaroveside A [(3S,4R,5Z,7E)-3,4-dihydroxy-5,7-megastigmadien-9-one-3-O-β-D-glucopyranoside] (1), komaroveside B [(3S,4S,5S,6R,7E)-5,6-epoxy-3,4-dihydroxy-7-megastigmen-9-one-3-O-β-D-glucopyranoside] (2) and komaroveside C [(3S,4S,5S,6R,7E,9S)-5,6-epoxy-3,4,9-trihydroxy-7-megastigmen-3-O-β-D-glucopyranoside] (3) were isolated, together with eight known compounds, from Cardamine komarovii. The identification of these compounds and the elucidation of their structures were based on 1D- and 2D-NMR spectral data analysis. The isolated compounds were tested for their cytotoxicity against four human tumor cell lines (A549, SK-OV-3, SK-MEL-2, HCT15) in vitro using the sulforhodamine B bioassay.     

Studies of the constituents of Gardenia species. II. Terpenoids from Gardeniae Fructus

Four new terpenoids, gardenate A (1), 2-hydroxyethyl gardenamide A (2), (1R,7R,8S,10R)-7,8,11-trihydroxyguai-4-en-3-one 8-O-beta-D-glucopyranoside (3) and Jasminoside F (4), were isolated from Gardeniae Fructus. Their structures were established on the basis of spectral analysis.     

Synthesis of (+)-uniflorine a: a structural reassignment and a configurational assignment

The total synthesis of (+)-uniflorine A has allowed for the structural reassignment and the configurational assignment of the alkaloid (-)-uniflorine A from a 1,2,6,7,8-pentahydroxyindolizidine structure to (-)-(1 R,2 R,3 R,6 R,7 S,7a R)-1,2,6,7-tetrahydroxy-3-hydroxymethylpyrrolizidine (6- epi-casuarine).     

Formal total synthesis of (+)-macrosphelide A based on regioselective hydrolysis using lipase

Three kinds of seco-macrosphelide A congeners, (4R,5S,10R,11S,15S)-6, (4R,5S,9S,14R,15S)-7 and (3S,8R,9S,14R,15S)-8 were chemically synthesized, and they were exposed to the lipase OF-360 from Candida rugosa to give three hydroxy carboxylic acids, respectively. Macrolactonization of the hydroxy acid (4R,5S,10R,11S)-18 derived from (4R,5S,10R,11S,15S)-6 gave 12-membered lactone (19) in 47% overall yield from 6, while that of the seco-acid (4) derived from (4R,5S,9S,14R,15S)-7 afforded (-)-dibenzyl macrosphelide A (25) in 27% overall yield from 7. Macrolactonization of the hydrolysis product, seco-acid (5) derived from (3S,8R,9S,14R,15S)-8, provided (-)-dibenzyl macrosphelide A (25) (5% overall yield from 8) and 12-membered lactone (19) (20% overall yield from 8) concurrently.     

Synthesis and antiviral activities of N-mono- and/or N,N'-di-carbamoyl and acyl derivatives of symmetrical diamines

N-carbamoyl and N-acyl diamine derivatives were synthesized from symmetrical diamines by their addition to iso(thio)cyanates, cleavage reaction of acid anhydride, or N-acylation by acyl chloride. (1R,2R)-1,2-Diaminocyclohexane [(1R,2R)-1], meso-1,2-diaminocyclohexane (meso-1), (1R,2R)-1,2-diphenylethylenediamine [(1R,2R)-3], or meso-1,2-diphenylethylenediamine (meso-3) were used as the starting symmetrical diamines. The target compounds synthesized herein were evaluated for antiviral activity with herpes simplex virus type 1 (HSV-1). A few derivatives of 1,2-diaminocyclohexane [(1R,2R)-7aa and cis-7b] with adamantyl group(s) showed significant antiviral activity (EC(50)=16.0, 27.0 microg/ml).     

Synthesis,structure, and reactivity of some sterically hindered (Silylamino)phosphines

A series of new (silylamino)phosphines that contain sterically bulky silyl groups on nitrogen were prepared by deprotonation/substitution reactions of the hindered disilylamines t-BuR(2)Si(Me(3)Si)NH (1, R = Me; 2, R = Ph) and (Et(3)Si)(2)NH (3). Sequential treatment of the N-lithio derivatives of 1-3 with PCl(3) or PhPCl(2) and MeLi gave the corresponding (silylamino)phosphines t-BuR(2)Si(Me(3)Si)NP(R')Me (5, R = Me, R' = Ph; 6, R = Ph, R' = Me) and (Et(3)Si)(2)NP(R)Me (11, R = Me; 12, R = Ph) in high yields. Two of the P-chloro intermediates t-BuR(2)Si(Me(3)Si)NP(Ph)Cl (7, R = Ph; 9, R = Me) were also isolated and fully characterized. Hydrolysis of 7 afforded the crystalline PH-substituted aminophosphine oxide t-BuPh(2)SiN(H)P(Ph)(=O)H (10). Thermal decomposition of 7 occurred with elimination of Me(3)SiCl and formation of a novel P(2)N(2) four-membered ring system (36) that contains both P(III) and P(V) centers. Reactions of the N-lithio derivatives of amines 1 and 2 with phosphorus trihalides afforded the thermally stable -PF(2) derivatives t-BuR(2)Si(Me(3)Si)NPF(2) (13, R = Me; 14, R = Ph) and the unstable -PCl(2) analogue 17 (R = Ph). Reduction (using LiAlH(4)) of the SiPh-substituted dihalophosphines 14 and 17 gave the unstable parent phosphine t-BuPh(2)Si(Me(3)Si)NPH(2) (15). The P-organo-substituted (silylamino)phosphines underwent oxidative bromination to afford high yields of the corresponding N-silyl-P-bromophosphoranimines t-BuR(2)SiN=P(R')(Me)Br (18, R = R' = Me; 19, R = Me, R' = Ph; 20, R = Ph, R' = Me) and Et(3)SiN=P(R)(Me)Br (23, R = Me; 24, R = Ph). Subsequent treatment of these reactive PBr compounds with lithium trifluoroethoxide or phenoxide produced the corresponding PO derivatives t-BuR(2)SiN=P(R')(Me)OR' ' (25 and 26, R' ' = CH(2)CF(3); 28-30, R' ' = Ph) and Et(3)SiN=P(R)(Me)OR' (31 and 33, R' = CH(2)CF(3); 32 and 34, R = Ph), respectively. Many of the new compounds containing the bulky tert-butyldiphenylsilyl group, t-BuPh(2)Si, were solids that gave crystals suitable for X-ray diffraction studies. Consequently, the crystal structures of three (silylamino)phosphines (6, 7, and 14), one (silylamino)phosphine oxide (10), one N-silylphosphoranimine (30), and the cyclic compound 36 were determined. Among the (silylamino)phosphines, the P-N bond distances [6, N-PMe(2), 1.725(3) A; 7, N-P(Ph)Cl, 1.68(1) A, 14, N-PF(2), 1.652(4) A] decreased significantly as the electron-withdrawing nature of the phosphorus substituents increased. The N-silylphosphoranimine t-BuPh(2)SiN=PMe(2)OPh (30), which is a model system for poly(phosphazene) precursors, had a much shorter P=N distance of 1.512(6) A and a wide Si-N-P bond angle of 166.4(3) degrees. A similar P=N bond distance [1.514(7) A] and Si-N-P angle [169.9(6) degrees ] were observed for the exocyclic P=N-Si linkage in the ring compound 36, while the phosphine oxide 10 had P-N and P=O distances of 1.637(4) and 1.496(3) A, respectively, and a Si-N-P angle of 134.3(2) degrees.     

A novel iridoid from Boschniakia rossica

A novel iridoid, (4R)-4-hydroxymethylboschnialactone (1), has been isolated from Boschniakia rossica, together with three previously known compounds, (24S)-3beta-hydroxy-24-ethylcholest-5-en-7-one (2), (24R)-3beta-hydroxy-24-ethylcholest-5-en-7-one (3) and methyl p-coumarate, using column chromatography. The structures of compounds were elucidated by spectroscopic methods.     

Sesquiterpenoid derivatives from Ferula ferulaeoides [correction of ferulioides]. V

Nine novel prenyl-dihydrofurocoumarin-type sesquiterpenoid derivatives, 2,3-dihydro-7-hydroxy-2R*,3R*-dimethyl-2-[4,8-dimethyl-3(E),7-nonadienyl]-furo[3,2-c]coumarin, 2,3-dihydro-7-hydroxy-2S*,3R*-dimethyl-2-[4,8-dimethyl-3(E),7-nonadien-6-onyl]-furo[3,2-c]coumarin, 2,3-dihydro-7-hydroxy-2S*,3R*-dimethyl-2-[4-methyl-5-(4-methyl-2-furyl)-3(E)-pentenyl]-furo[3,2-c]coumarin, 2,3-dihydro-7-hydroxy-2R*,3R*-dimethyl-2-[4-methyl-5- (4-methyl-2-furyl)-3(E)-pentenyl]-furo[3,2-c]coumarin, 2,3-dihydro-7-methoxy-2S*,3R*-dimethyl-2-[4,8-dimethyl-3(E),7-nonadienyl]-furo[3,2-c]coumarin, 2,3-dihydro-7-methoxy-2R*,3R*-dimethyl-2-[4,8-dimethyl-3(E),7-nonadienyl]-furo[3,2-c]coumarin, 2,3-dihydro-7-methoxy-2S*,3R*-dimethyl-2-[4,8-dimethyl-3(E),7-nonadien-6-onyl]-furo-[3,2-c]coumarin, and 2,3-dihydro-7-methoxy-2S*,3R*-dimethyl-2-[4-methyl-5-(4-methyl-2-furyl)-3(E)-pentenyl]-furo[3,2-c]coumarin, were isolated from the roots of Ferula ferulaeoides [corrected]. The structures were established by comprehensive spectral analysis. The biosynthetic pathway leading to these prenyl-furocoumarin-type sesquiterpenoids is proposed based on their structures.     

Walsucochinoids A and B: new rearranged limonoids from Walsura cochinchinensis

Walsucochinoids A (1) and B (2), two rearranged limonoids possessing an unprecedented carbon framework, were isolated from Walsura cochinchinensis. Their configurations were assigned as 1S, 3R, 4R, 5R, 6R, 7S, 8R, 9R, and 10R on the basis of a detailed examination of spectroscopic data, single crystal X-ray diffraction analysis, and CD experiments.     

A new phenylethanoid glycoside from Isodon sculponeatus

A new phenylethanoid glycoside,seulponisidc(1) was isolated from the aerial parts of Isodon sculponeatus(Vaniot) Kudo, along with six known compounds martynoside(2),verbascoside(3),(+)-hydroxypinoresinol-8-O- β-D-glucoside(4),cedrusin(5), 7-megastigmene-3S,5R,6R,7E,9S-tetrol(6) and 4-oxo- β-ionol- β-D-glucopyranoside(7).Their chemical structures were elucidated from physieochemical data and by acidic hydrolysis.     

Neolignans from Piper futokadsura and their inhibition of nitric oxide production

From a MeOH extract of the aerial part of Piper futokadsura, the tetrahydrofuran lignans, futokadsurin A [(7S,8S,7'S,8'R)-3,4,3'-trimethoxy-4'-hydroxy-7,7'-epoxylignan], futokadsurin B [(7R,8R,7'R,8'S)-3,4-dimethoxy-3',4'-methylenedioxy-7,7'-epoxylignan], and futokadsurin C [(7R,8R,7'S,8'S)-3,4-methylenedioxy-3',4'-dimethoxy-7,7'-epoxylignan] were isolated, together with nine known neolignans. In addition, L-tryptophan, pellitorine, phytol, elemicin, and 1,2,4-trimethoxyphenyl-5-aldehyde were isolated. The structures of the new compounds were elucidated using spectroscopic methods. These lignans inhibited nitric oxide production by a murine macrophage-like cell line (RAW 264.7), which was activated by lipopolysaccharide and interferon-gamma.     

Transformation of arctiin to estrogenic and antiestrogenic substances by human intestinal bacteria

After anaerobic incubation of arctiin (1) from the seeds of Arctium lappa with a human fecal suspension, six metabolites were formed, and their structures were identified as (-)-arctigenin (2), (2R,3R)-2-(3',4'-dihydroxybenzyl)-3-(3",4"-dimethoxybenzyl)butyrolactone (3), (2R,3R)-2-(3'-hydroxybenzyl)-3-(3",4"-dimethoxybenzyl)butyrolactone (4), (2R,3R)-2-(3'-hydroxybenzyl)-3-(3"-hydroxy-4"-methoxybenzyl)butyrolactone (5), (2R,3R)-2-(3'-hydroxybenzyl)-3-(3",4"-dihydroxybenzyl)butyrolactone (6), and (-)-enterolactone (7) by various spectroscopic means including two dimensional (2D)-NMR, mass spectrometry, and circular dichroism. A possible metabolic pathway was proposed on the basis of their structures and the time course of the transformation. Enterolactones obtained from the biotransformation of arctiin and secoisolariciresinol diglucoside (SDG, from the seeds of Linum usitatissium) by human intestinal bacteria were proved to be enantiomers, with the (-)-(2R,3R) and (+)-(2S,3S) configurations, respectively. Compound 6 showed the most potent proliferative effect on the growth of MCF-7 human breast cancer cells in culture among 1 and six metabolites, while it showed inhibitory activity on estradiol-mediated proliferation of MCF-7 cells at a concentration of 10 microM. These results indicate that the transformation of 1 by intestinal flora might be essential for the manifestation of the estrogenic and antiestrogenic activity of 1.     

Ionic iron(iii) complexes of bis(phenol)-functionalized imidazolium cations: synthesis, structures and catalysis for aryl Grignard cross-coupling of alkyl halides

A series of bis(phenol)-functionalized imidazolium salts, 1,3-bis(4,6-di-R(1)-2-hydroxybenzyl)-2-R(2)-4,5-di-R(3)-imidazolium chlorides H(3)L(n)Cl (R(1) = (t)Bu, R(2) = R(3) = H, H(3)L(1)Cl, 1; R(1) = CH(3), R(2) = R(3) = H, H(3)L(2)Cl, 2; R(1) = (t)Bu, R(2) = H, R(3) = Cl, H(3)L(3)Cl, 3; R(1) = (t)Bu, R(2) = CH(3), R(3) = H, H(3)L(4)Cl, 4), were used to produce a novel series of ionic iron(iii) complexes [H(3)L(n)][FeX(4)] (n = 1, X = Cl, 5; n = 2, X = Cl, 6; n = 3, X = Cl, 7; n = 4, X = Cl, 8; n = 1, X = Br, 9; n = 3, X = Br, 10). All of the complexes were characterized by Raman spectroscopy and electrospray ionization mass spectrometry. Elemental analysis and X-ray crystallography were also used. All of the complexes were non-hygroscopic and air-stable, with five of them existing as solids (5, 7-10) and one as an oil (6) at room temperature. A preliminary catalytic study on the cross-coupling reactions of aryl Grignard reagents with primary and secondary alkyl halides bearing β-hydrogens, revealed that all of the ionic iron(iii) complexes exhibited good to excellent catalytic activity. Complexes 5, 6 and 8 exhibited optimal activity, whereas 7, 9 and 10 showed only moderate activity. Furthermore, by simply decanting the cross-coupling product in the ether layer, complexes 5 and 6 could be reused in at least seven successive runs without significant loss in catalytic activity.     

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.