Polyacetylene glycosides from Gymnaster koraiensis

Two polyacetylene glycosides, gymnasterkoreasides A and B, were isolated from the roots of Gymnaster koraiensis. Their structures were elucidated to be (3R)-8-decene-4,6-diyne-1,3-diol 1-O-beta-D-glucopyraside and (3R)-8-decene-4,6-diyne-1,3-diol 1-O-beta-D-apiofuranosyl-(1-->6)-beta-D-glucopyraside on the basis of spectroscopic analysis including COSY, HMQC, and HMBC experiments, as well as chemical methods, which confirmed the determination of a chiral center by the modified Mosher's method.     

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.     

New acetylenic glucosides from Carthamus tinctorius

Two new acetylenic glucosides, 4',6'-acetonide-8Z-decaene-4,6-diyne-1-O-beta-D-glucopyranoside named carthamoside A(1) (1) and 4,6-decadiyne-1-O-beta-D-glucopyranoside named carthamoside A(2) (2), along with one known acetylenic glucoside, 8Z-decaene-4,6-diyne-1-O-beta-D-glucopyranoside (3), have been isolated from the air-dried flower of Carthamus tinctorius, these structures have been identified on the basis of spectroscopic methods.     

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.     

Flavonoids and a new polyacetylene from Bidens parviflora Willd

Fifteen flavonoids, 1-7 and 9-16, and a polyacetylene, 8, were isolated from the ethanol extract of the dried whole plant of Bidens parviflora Willd. by various chromatographic techniques. Their structures have been elucidated on the basis of spectroscopic analyses and chemical studies. Compound 8 is new and was identified as 3-(R),8(E)-decene-4,6-diyne-1,3,10-triol. All the flavonoid compounds were isolated for the first time from this plant species.     

New sphingolipids and a sterol from a lobophytum species of the Indian ocean

Chemical investigation of a soft coral species of the genus Lobophytum has resulted in the isolation of three new sphingolipids--(2S,3S,4R)-2-nonadecanoylamino-octadecane-1,3,4-triol (1), (2S,3R,4E,8E)-[(2'R)-2'-hydroxyheptadecanoylamino]-4,8-octadecadiene-1,3-diol (2), 1-O-(beta-D-glucopyranosyl)-(2S,3R,4E,8E)-2-[(2'R)-2'-hydroxynonadecanoylamino]-9-methyl-4,8-octadecadiene-1,3-diol (3) and a sterol--(24S)-ergost-5-en-3beta,7beta-diol (4) along with the known sphingolipid--(2S,3R,4E,8E)-2-hexadecanoylamino-4,8-octadecadien-1,3-diol (5) which showed cytotoxicity against human peripheral blood mononuclear cells (PBMC).     

Glycosides of Atractylodes ovata

A new coumarin glycoside and a new glycoside of an acetylene derivative were isolated from the water-soluble portion of the methanolic extract of Atractylodes ovata rhizome together with eight known compounds. Their structures were characterized as scopoletin beta-D-xylopyranosyl-(1-->6)-beta-D-glucopyranoside and (2E)-2-decene-4,6-diyne-1,8-diol 8-O-beta-D-apiofuranosyl-(1-->6)-beta-D-glucopyranoside, respectively, based on chemical and spectroscopic investigations. A comparison of the polar constituents among Atractylodes japonica, Atractylodes lancea, and A. ovata is led to the conclusion that A. ovata is distinguishable from A. lancea and A. japonica, as also shown by phylogenetic analysis.     

Ceramide constituents from five mushrooms

Five mushrooms, Panellus serotinus, Lyophyllum connatum, Amanita pantherina, Sarcodon aspratus and Lepista nuda, have been investigated chemically. Two new ceramides, (2S,3R,4E,8E)-N-hexadecanoyl-2-amino-9-methyl-4,8-octadecadiene-1,3-diol (1) and (2S,3R,4E,8E,9'Z,12'Z)-N-9',12'-octadecadienoyl-2-amino-9-methyl-4,8-octadecadiene-1,3-diol (2), have been isolated from Panellus serotinus. Compound 2 was also isolated from Lyophyllum connatum. Two new ceramides, (2S,2'R,3R,4E,8E)-N-2'-hydroxypentadecanoyl-2-amino-9-methyl-4,8-octadecadiene-1,3-diol (4) and (2S,2'R,3R,4E,8E)-N-2'-hydroxytetradecanoyl-2-amino-9-methyl-4,8-octadeca-diene-1,3-diol (5), have been isolated from Amanita pantherina with (2S,2'R,3R,4E,8E)-N-2'-hydroxyhexadecanoyl-2-amino-9-methyl-4,8-octadecadiene-1,3-diol (3), a known synthetic compound. Compounds 3 and 4 were also isolated from Sarcodon aspratus and compound 3 was isolated from Lepista nuda. The structures of the new compounds were elucidated on the basis of their spectral data.     

Synthesis of new trans double-bond sphingolipid analogues: Delta(4,6) and Delta(6) ceramides

Unsaturation was introduced at Delta(4,6) and Delta(6) of the sphingoid chain of naturally occurring ceramide 1 via a beta-keto sulfoxide (12) and sulfone (18) derived from N-Boc-L-serine methyl ester acetonide (9), affording two novel ceramide analogues, (2S,3R)-2-octanoylamidooctadeca-(4E,6E)-diene-1,3-diol (2) and (2S,3R)-2-octanoylamidooctadec-(6E)-ene-1,3-diol (3). After C-alkylation of 12 with (E)-1-bromo-2-tetradecene (8), a trans double bond was installed by elimination of PhS(O)H, providing conjugated dienone oxazolidine 13. Reaction of 18 with 8, followed by desulfonation (Al(Hg)), afforded keto-oxazolidine 20, which bears a (E)-Delta(6) double bond. The syntheses of analogues 2 and 3 from ketones 13 and 20, respectively, were completed by the following sequence of reactions: diastereoselective reduction (NaBH(4)/CeCl(3) or DIBAL-H), hydrolysis of the oxazolidine ring, liberation of the amino group, and installation of the N-amide group.     

A new acetylenic compound from the rhizomes of Atractylodes chinensis and its absolute configuration

A new acetylenic compound "atractyloyne", (3S,4E,6E,12E)-1-isovaleryloxy-tetradeca-4,6,12-triene-8,10-diyne-3,14-diol (1) was isolated from the rhizomes of Atractylodes chinensis (Compositae) together with a known compound (4E,6E,12E)-3-isovaleryloxy-tetradeca-4,6,12-triene-8,10-diyne-1,14-diol (2). These structures were determined on the basis of the spectroscopic data and chemical evidence, and the absolute configuration of 1 was established by the modified 2-methoxy-2-trifluoromethylphenylacetic acid (MTPA) method.     

Antibacterial activity of phytochemicals isolated from Atractylodes japonica against methicillin-resistant Staphylococcus aureus

Methicillin-resistant Staphylococcus aureus (MRSA) has been emerging worldwide as one of the most important problems in communities and hospitals. Therefore, new agents are needed to treat acute oral infections from MRSA. In this study, antibacterial compounds from the roots of Atractylodes japonica (A. japonica) were isolated and characterized. The compounds were isolated from the root extracts using HPLC-piloted activity-guided fractionations. Four A. japonica compounds were isolated and identified as atractylenolide III (1), atractylenolide I (2), diacetylatractylodiol [(6E,12E)-tetradeca-6,12-diene-8,10-diyne-1,3-diol diacetate, TDEYA, 3). and (6E,12E)-tetradecadiene-8,10-diyne-1,3-diol (TDEA, 4), which was obtained by hydrolysis of TDEYA. The minimum inhibitory concentrations (MICs) was determined in the setting of clinical MRSA isolates. Compound 4 showed anti-MRSA activity with a MIC value of 4-32 μg/mL. The overall results provide promising baseline information for the potential use of the extract of A. japonica as well as some of the isolated compounds in the treatment of bacterial infections.     

Turpinionosides A-E: megastigmane glucosides from leaves of Turpinia ternata Nakai

From leaves of Turpenia ternata (Staphylaceae), one megastigmane and seven of its glucosides (1-8) were isolated. Megastigmane and two of the glucosides were found to be known compounds, namely, 3S,5R,6R,9S-tetrahydroxymegastigmane (1), corchoionoside C (2), and icariside B4 (3). The structures of compounds 4-8 (turpinionosides A-E, respectively) were elucidated by means of spectroscopic analyses, and then their absolute structures were determined by the modified Mosher's method to be (3S,5R,6S,9S)-3,6,9-trihydroxymegastigman-7-ene 3-O- and 9-O-beta-D-glucopyranosides (4, 5, respectively), (1S,3S,5R,6S,9R)-3,9,12-trihydroxymegastigmane 3-O-beta-D-glucopyranoside (6), (3S,4R,9R)-3,4,6-trihydroxymegastigman-5-ene 3-O-beta-D-glucopyranoside (7), and (2S,9R)-2,9-dihydroxymegastigman-5-en-4-one 2-O-beta-D-glucopyranoside (8).     

Two new glycosides from the whole plants of Glechoma hederacea L

Two new glycosides, 7S,7'S,8R,8'R-icariol A(2)-9-O-beta-D-glucopyranoside (1) and 4-allyl-2-hydroxyphenyl 1-O-beta-D-apiosyl-(1-->6)-beta-D-glucopyranoside (2), were isolated from the dried whole plants of Glechoma hederacea L. (Labiatae) together with four known compounds, cistanoside E (3), dihydrodehydrodiconiferyl alcohol 4-O-beta-D-glucopyranoside (4), apigenin 7-O-beta-D-glucuronopyranoside (5) and luteolin 7-O-beta-D-glucopyranoside (6). The structures of the new compounds were elucidated on the basis of chemical and spectral analysis.     

A Chemical Study of Burley Tobacco Flavour (Nicotiana tabacum L.) VII. Identification and synthesis of twelve irregular terpenoids,related to solanone,including 7,8-dioxabicyclo[3.2.1]octane and 4,9-dioxabicyclo[3.3.1]nonane derivatives

Twelve novel constituents isolated from Burley tobacco condensate by semi-preparative GLC. have been identified as (E)-3,4-epoxy-5-isopropyl-nonane-2,8-dione ( A ), exo-(1-methyl-4-isopropyl-7,8-dioxabicyclo[3.2.1]oct-6-yl)methyl ketone ( B ), exo-1-(1-methyl-4-isopropyl-7,8-dioxabicyclo[3.2.1]oct-6-yl)-ethanol ( C ), (E)-5-isopropyl-8-hydroxy-8-methyl-non-6-en-2-one ( D ), (E)-5-isopropyl-6,7-epoxy-8-hydroxy-8-methyl-nonan-2-one ( E ), endo-2-(1-methyl-4-isopropyl-7,8-dioxabicyclo[3.2.1]oct-6-yl)-propan-2-ol ( F ), 3,3,5-trimethyl-8-isopropyl-4,9-dioxabicyclo[3.3.1]nonan-2-ol ( G ), (E)-5-isopropyl-non-3-ene-2,8-diol ( H ), 5-isopropyl-nonane-2,8-diol ( I ), (E)-5-isopropyl-8-hydroxy-non-6-en-2-one ( J ), 5-isopropyl-8-hydroxy-nonan-2-one ( K ), and (E)-3-isopropyl-6-methyl-hepta-4,6-dien-1-ol ( L ). Compounds A–K were synthesized from norsolanadione ( 2 ), and compound L from 2-isopropyl-5-oxo-hexanal ( 15 ). The relative configuration of the bicyclic internal acetals B, C, F, G and their δ-keto-epoxide precursors A and E is discussed. All these Burley tobacco flavour components belong to a growing family of metabolites structurally related to solanone ( 1 ). They are believed to arise from the breakdown of cembrene-type precursors.     

Synthesis of a library of stereo- and regiochemically diverse aminoglycoside derivatives

A library of forty modified aminoglycosides was prepared in which the configuration and regiochemistry of two or three rings was widely varied. The library was based around three core ring systems: the 2-deoxystreptamine ring system found in the natural products, and both enantiomers of (1R*,2R*,4R*,5R*)-2,5-diamino-cyclohexane-1,4-diol and (1R*,3R*,4R*,6R*)-4,6-diaminocyclohexane-1,3-diol. In each case, the core was modified by glycosylation with one or two sugar rings. The absolute configuration of the sugar substituents (d or l), the configuration of the anomeric centres (alpha or beta), and the regiochemical arrangement of the amine(s) were varied.     

Chemical constituents from the colombian medicinal plant Niphogeton ternata

Two coumarins and one polyacetylene, 5-0-(3-chloro-2-hydroxy-3-methylbutyl)-8-methoxypsoralen (1), 2',3'-dihydro-jatamansin (2), and 10-chloro-1-heptadecene-4,6-diyne-3,8,9-triol (3), along with 15 known compounds (4-18), were isolated from the methanol extract of Niphogeton ternata. Their structures were elucidated by spectroscopy.     

New alpha-tetralonyl glucosides from the fruit of Juglans mandshurica

Five new alpha-tetralonyl glucosides, juglanosides A-E (1-5) were isolated from the fresh rejuvenated fruit of Juglans mandshurica. Their structures were elucidated as (4S)-4-hydroxy-alpha-tetralone 4-O-beta-D-glucopyranoside (1), (4S)-4,5-dihydroxy-alpha-tetralone 4-O-beta-D-glucopyranoside (2), (4S)-4,6-dihydroxy-alpha-tetralone 4-O-beta-D-glucopyranoside (3), (4S)-4,5,8-trihydroxy-alpha-tetralone 4-O-beta-D-glucopyranoside (4), and (4S)-4,5,8-trihydroxy-alpha-tetralone 5-O-beta-D-glucopyranoside (5) on the basis of spectroscopic analysis and chemical evidence.     

Cerebrosides from the roots of Serratula chinensis

A new cerebroside, 1-O-beta-D-glucopyranosyl-(2S,3R,8E)-2-[(2'R)-2-hydroxy- palmitoylamino]-8-octadecene-1,3-diol, along with aralia cerebroside and 1-O-beta-D- glucopyranosyl-(2S,3S,4R,8E)-2-[(2'R)-2-hydroxybehenoylamino]-8-octadecene-1,3,4-triol were isolated from the roots of Serratula chinensis S. Moore. The structure of the new cerebroside was established by spectroscopic and chemical means. Occurrence of cerebrosides in Serratula is reported here for the first time.     

Antibacterial sphingolipid and steroids from the black coral Antipathes dichotoma

From the black coral Antipathies dichotoma, a sphingolipid (2S*,3S*,4E,8E)-2N-[tetradecanoyl]-4(E),8(E)-icosadiene-1,3-diol (1) and a steroid (22E)-methylcholesta-5,22-diene-1α,3β,7α-triol (2) were isolated. Other known compounds, 3β,7α-dihydroxy-cholest-5-ene (3), (22E,24S),5α,8α-epidioxy-24-methylcholesta-6,22-dien-3β-ol (4) and (22E,24S),5α,8α-epidioxy-24-methylcholesta-6,9(11),22-trien-3β-ol (5). The structures were established on the basis of NMR spectroscopic analysis and comparison with literature. The antibacterial activity of five compounds was evaluated.     

Five new nortropane alkaloids and six new amino acids from the fruit of Morus alba LINNE growing in Turkey

Investigation of the constituents of the fruits of Morus alba LINNE (Moraceae) afforded five new nortropane alkaloids (1-5) along with nor-psi-tropine (6) and six new amino acids, morusimic acids A-F (7-12). The structures of the new compounds were determined to be 2alpha,3beta-dihydroxynortropane (1), 2beta,3beta-dihydroxynortropane (2), 2alpha,3beta,6exo-trihydroxynortropane (3), 2alpha,3beta,4alpha-rihydroxynortropane (4), 3beta,6exo-dihydroxynortropane (5), (3R)-3-hydroxy-12-[(1S,4S)-4-[(1S)-1-hydroxyethyl]-pyrrolidin-1-yll-dodecanoic acid-3-O-beta-D-glucopyranoside (7), (3R)-3-hydroxy-12-[(1S,4S)-4-[(1S)-1-hydroxyethyl]-pyrrolidin-1-yll-dodecanoic acid (8), (3R)-3-hydroxy-12-1(1R,4R,5S)-4-hydroxy-5-methyl-piperidin-1-yll-dodecanoic acid-3-O-beta-D-glucopyranoside (9), (3R)-3-hydroxy-12-[(1R,4R,5S)-4-hydroxy-5-methyl-piperidin-1-yll-dodecanoic acid (10), (3R)-3-hydroxy-12-[(1R,4R,5S)-4-hydroxy-5-hydroxymethyl-piperidin-1-yl]-dodecanoic acid-3-O-beta-D-glucopyranoside (11), and (3R)-3-hydroxy-12-[(1R,4S,5S)-4-hydroxy-5-methyl-piperidin-1-yl]-dodecanoic acid (12) on the basis of spectral and chemical data.