A triterpenoid saponin from Phytolacca esculenta.

A new triterpenoid saponin, 3-O-[beta-D-glucopyranosyl(1----4)-beta-D- xylopyranosyl]-28-O-beta-D-glucopyranosyl-30-methyloleanate-9(11), 12-dien- 2,3,23-trihydroxyl-28-oic acid, was isolated from the roots of Phytolacca esculenta. The structure was assigned by chemical methods and spectral analysis (1H, 13C, DEPT NMR, EIMS and FABMS) including 1H-1H COSY, 1H-13C COSY and 1H-1H NOESY.     

黄射干的异黄酮类成分

从黄射干Ｉｒｉｓｔｅｃｔｏｒｕｍ的甲醇抽提物中分到５个异黄酮：鸢尾黄酮甲素（１）,鸢尾花素（２）,野鸢尾黄酮（３）,鸢尾黄酮（４）,鸢尾黄酮甙（５）。化合物（１）和（２）系首次从黄射干中分到。所有成分经详细光谱分析确定。     

Alkaloids from Toddalia aculeata

Two alkaloids N-methyl-4-hydroxy-7-methoxy-3-(2,3-epoxy-3-methylbutyl)-1H-quinolin-2-one (1) and 3-(2,3-dihydroxy-3-methylbutyl)-4,7-dimethoxy-1-methyl-1H-quinolin-2-one (2a) have been isolated from CH(2)Cl(2):methanol (1:1) and methanol extracts of leaves and stems of Toddalia aculeata. Their structures along with that of 15 other compounds, of which three are isolated for the first time from genus Toddalia, were established by their detailed spectral studies including 2D NMR viz. (1)H-(1)H COSY, (1)H-(13)C COSY, and HMBC.     

栗柄金粉蕨的黄酮类成分

从栗柄金粉蕨（ Ｏｎｙｃｈｉｕｍ ｌｕｃｉｄｕｍ ） 地上部分的甲醇抽提物中分到１０ 个成分, 经详细的一维、二维核磁数据分析, 它们被鉴定为： 木犀草甙（１） , ３ , ７ － 二甲基槲皮素（２） , 高山甙Ｂ （３） , 金粉蕨素（４） , 栗柄醇（５） , 金粉蕨醇Ｂ（６） , β－ 谷甾醇（７） , 胡萝卜甙（８） ,齐墩果酸（９） 和蔗糖（１０） 。栗柄醇系新成分。１ , ２, ９ 系首次由金粉蕨属分到。     

Buzonamine, a new alkaloid from the defensive secretion of the millipede, Buzonium crassipes

GC-MS analysis of the defensive secretion from the millipede Buzonium crassipes showed three volatile components, beta-pinene (35%), limonene (6%) and a new alkaloid, buzonamine (59%). Buzonamine had an HRMS molecular ion at m/z=221.1785 (calculated for C(14)H(23)NO, 221.1781), 14 carbons in the 13C-NMR and 23 hydrogens by SFORD, DEPT and APT experiments. All distinct 1H nuclei were assigned to 13C resonances with 2D 1H-13C COSY data, and the final structure was determined by 1H-1H COSY, 1H-13C HMBC and nOe experiments. Buzonamine contains four rings including an epoxy group and a tertiary nitrogen. beta-Pinene, limonene or buzonamine, kept the mound nesting ant, Formica obscuripes, from eating mealworms (Tenebrio molitor) treated with 1mg of the chemical. A 150mg millipede expels 4mg of secretion.     

Clitolactone: a banana slug antifeedant from Clitocybe flaccida

Clitolactone, 5-(chloromethyl)-3-methyl-2(5H)-furanone, was isolated from sporocaps of the mushroom Clitocybe flaccida. The structure was determined by HRMS, EIMS, (1)H & (13)C NMR, 2D (1)H-(13)C COSY and (1)H-(1)H COSY. This mushroom is not eaten by the banana slug Ariolimax columbianus (Gould), a mycophagist from the temperate rain forests of the Pacific Northwest. Clitolactone acts as an antifeedant because these slugs rejected 1.0 cm(2) pieces of lettuce treated with 25 μg of clitolactone.     

The conversion of 3-C-beta-D-galactopyranosyl phloroacetophenone to a spiroketal derivative

Treatment of 3-C-beta-D-galactopyranosylphloroacetophenone in hot water with a catalytic amount of p-toluenesulfonic acid afforded a spiroketal compound as the main product. The chirality of the spiro carbon of the product was R, which is the opposite of the spiroketal obtained by the conversion of 3-C-beta-D-glucopyranosyl phloroacetophenone under identical conditions. The structure was determined by 1H-1H COSY, 1H-13C COSY, NOESY and HMBC spectroscopy.     

Kaempferol glycosides from Hosta ventricosa.

Leaves of Hosta ventricosa yielded eight kaempferol glycosides, of which six: the 3-(2G-glucosylrutinoside)-7-glucoside, 3-sophoroside-7-glucoside, 3-rutinoside-7-glucoside, 3-(2G-glucosylrutinoside), 3-sophoroside, 3-rutinoside were fully characterized and two: the 3-xylosylrutinoside-7-glucoside and 3-xylosylrutinoside were tentatively identified. Investigations included 1H-1H COSY and 1H-1H 2D J NMR analysis.     

A New Diterpene Glycoside in Aster ageratoides Turcz.

A new natural diterpene glycoside was isolated from Aster ageratoides Turcz. Its structure was elucidated by means of IR, MS (FAB, EI), NMR (1H-, 13C-, DEPT), 2D-NMR (1H-1H COSY, 13C-1 H COSY, J-resolved, CoLoC) spectra and chemical method as 16β, 17-dihydroxy- (—) -kauran- 19-oic acid-β-D-glucopyanosyl ester.     

Two-dimensional concurrent HMQC-COSY as an approach for small molecule chemical shift assignment and compound identification

Chemical shift assignment is the first step toward the structure elucidation of natural products and other chemical compounds. We propose here the use of 2D concurrent HMQC-COSY as an experiment for rapid chemical shift assignment of small molecules. This experiment provides well-dispersed (1)H-(13)C peak patterns that are distinctive for different functional groups plus (1)H-(1)H COSY connectivities that serve to identify adjacent groups. The COSY diagonal peaks, which are phased to be absorptive, resemble (1)H-(13)C HMQC cross peaks. We demonstrate the applicability of this experiment for rapidly and unambiguously establishing correlations between different functional groups through the analysis of the spectrum of a metabolite (jasmonic acid) dissolved in CDCl(3). In addition, we show that the experiment can be used to assign spectra of compounds in a mixture of metabolites in D(2)O.     

A dimeric ArC2 compound from Peperomia pellucida

Pellucidin A, a novel dimeric ArC2 compound, together with dill-apiol have been isolated from the aerial parts of Peperomia pellucida. The structure of pellucidin A was established by 1D and 2D NMR spectroscopy (1H-1H COSY; 1H-13C COSY; DEPT; NOESY and double irradiation) and other spectroscopic techniques. The biogenesis of pellucidin A is also briefly discussed.     

Salvidorol, a nor-abietane diterpene with a rare carbon skeleton and two abietane diterpene derivatives from Salvia dorrii

Salvidorol (1), a irregular nor-abietane-type diterpene, was isolated from the aerial parts of Salvia dorrii, in addition to two epimeric abietane diterpenes (2 and 3). This is the first report of a nor-diterpene with an irregular skeleton. The structures were established by high-field NMR techniques ((1)H-(1)H COSY, DEPT, HMQC, HMBC, NOESY and HRMS) and in case of 2 was confirmed by X-ray analysis.     

Synthesis, complete characterization, and enantioselective electrokinetic separation of functionalized ruthenium complex enantiomers

Electrokinetic chromatography was employed to separate the enantiomers of two novel functionalized ruthenium(II) complexes with different polypyridyl coordination spheres. The use of anionic carboxymethyl-beta-cyclodextrin as chiral mobile phase additive resulted in maximum efficiency and resolution for the enantiomer separation of both transition metal complexes. The syntheses of the [4-(3-hydroxypropyl)-4'-methyl-2,2'-bipyridine]-bis(2,2'-bipyridine)rethenium(II)-bis(tetrafluoroborate) and [4-(3-hydroxypropyl)-4'-methyl-2,2'-bipyridine]-bis(4,4'-dimethyl-2,2'-bypyridine)ruthenium(II)-bis(tetrafluoroborate) complexes and their complete characterization by means of two-dimensional (1)H and (13)C[(1)H] NMR techniques ((1)H-(1)H COSY and (1)H-(13)C HMQC) as well as elemental analyses and MALDI-TOFMS are described in detail. The functionalized complexes can be used as building blocks for further reactions with polymers, biopolymers, surfaces and nanoparticles.     

Novel triterpenoid acyl esters and alkaloids from Anoectochilus roxburghii

Two novel sorghumol acyl esters, sorghumol 3-O-Z-p-coumarate and sorghumol 3-O-E-p-coumarate, and a novel alkaloid, anoectochine, were isolated from the whole plants of Anoectochilus roxburghii along with one known triterpenoid, sorghumol. Their structures were established by their detailed spectral studies, including two-dimensional NMR ((1)H-(1)H COSY, HSQC and HMBC).     

Diterpene glucosides from Pieris formosa

Five diterpene glucosides, pierisformosides B-F were isolated from Pieris formosa D. Don (Ericaceae). Their structures were elucidated on the basis of spectral analysis. including 1H-1H COSY, 13C-1H COSY, HMBC and NOESY experiments.     

Cladocalol, a pentacyclic 28-nor-triterpene from Eucalyptus cladocalyx with cytotoxic activity

A formylated triterpene named cladocalol has been isolated from the leaves of Eucalyptus cladocalyx, together with ursulolactone acetate, ursolic acid, 3 beta-acetate-12,20(29)-lupadien-28-oic acid, beta-sitosterol and the known flavonoid eucalyptine. Their structures were mainly established by extensive NMR studies (1H NMR, 13C NMR, DEPT, 1H-1H COSY, HSQC, HMBC) and mass spectroscopy as well as by X-ray crystallographic analysis. In this paper, we report on the cytotoxic effect induced by cladocalol and its derivatives on the myeloid leukemia cell line HL-60.     

Glycosylamines of 4,6-O-butylidene-alpha-D-glucopyranose: synthesis and characterization of glycosylamines, and the crystal structure of 4,6-O-butylidene-N-(o-chlorophenyl)-beta-D-glucopyranosylamine

A total of nine glycosylamines of 4,6-O-butylidene-alpha-D-glucopyranose were synthesized using primary amines having various groups in their ortho- or para-positions. Among these, six are monoglycosylamines, including one primary glycosylamine, and three are bis-glycosylamines. All these compounds were characterized by 1H, 1H-1H COSY, 1H-13C COSY and 13C NMR spectroscopy and FTIR spectra. The FAB mass spectra provided the molecular weights of the products by exhibiting the corresponding molecular ion peaks. The crystal structure of 4,6-O-butylidene-N-(o-chlorophenyl)-beta-D-glucopyranosylamine revealed the C-1 glycosylation, the beta-anomeric nature, and the 4C1 chair conformation of the saccharide unit in the product. In the lattice two types of dimers exist. While one type of dimer is formed through O-H...O type of interactions, the other type is formed via C-H...O type of interactions. In the direction of these C-H...O type of interactions, the dimeric units are connected to form a chain.     

Two Novel Diterpenoid Alkaloids Isolated from the Roots of Aconitum brevicalcaratum

Two new diterpenoid alkaloids were isolated from the roots of Aconitum brevicalcaratum Diels. They were acobretine D ( Ⅰ )and acobretine E ( Ⅱ ), and the structures of which were identified on the basis of spectroscopic evidences (IR, MS, 1 H and 13C-NMR) and confirmed by chemical transformations. The 1 H and 13C chemical shifts of the hydrochloride of Ⅰ were assigned in relation to of 1 H-1 H COSY and 13C-1 H COSY.     

假地枫皮中二萜酸类化合物研究

从八角属植物假地枫皮的石油醚提取物中分离出5个二萜酸类化合物,经波谱数据分析(^1H NMR、^13C NMR、^1H-^1H COSY、NOESY、HSQC和HMBC),分别鉴定为4-epi-dehydroabietic acid(1)、4-epi-sandaraeopinaric acid(2)、4-epi-abietic acid(3)、4-epi-isopimaric acid(4)和8,11,13,15-abietatetraen-19-oic acid(4)。     

Re-characterization of three conjugated linolenic acid isomers by GC-MS and NMR

Conjugated linolenic acids (CLN) refer to a group of octadecatrienoic acids with three conjugated double bonds. Minor positional and geometrical differences among CLN isomers make their separation and identification difficult. We have used GC-MS and NMR to study three common CLN isomers namely alpha-eleostearic acid, beta-eleostearic acid and punicic acid, finding that some signals of olefinic carbon atoms in NMR spectra were mistakenly assigned in the literature. The present study was therefore undertaken to re-characterize the location of CC double bonds and assign the chemical signals of proton and carbon atoms using (1)H NMR, (13)C NMR, (1)H-(1)H two-dimensional correlation spectra ((1)H-(1)H COSY) and (13)C-(1)H two-dimensional correlation spectra ((13)C-(1)H COSY). The geometrical structure of double bonds in these three CLN isomers was identified using homonuclear decoupling technique.