Four New Podocarpane‐Type Trinorditerpenes from Aleurites moluccana

Four new podocarpane‐type trinorditerpenenes, (5β,10α)‐12,13‐dihydroxypodocarpa‐8,11,13‐trien‐3‐one ( 1 ), (5β,10α)‐12‐hydroxy‐13‐methoxypodocarpa‐8,11,13‐trien‐3‐one ( 2 ), (5β,10α)‐13‐hydroxy‐12‐methoxypodocarpa‐8,11,13‐trien‐3‐one ( 3 ), and (3α,5β,10α)‐13‐methoxypodocarpa‐8,11,13‐triene‐3,12‐diol ( 4 ), together with four known diterpenes, 12‐hydroxy‐13‐methylpodocarpa‐8,11,13‐trien‐3‐one ( 5 ), spruceanol ( 6 ), ent‐3α‐hydroxypimara‐8(14),15‐dien‐12‐one ( 7 ), and ent‐3β,14α‐hydroxypimara‐7,9(11),15‐triene‐12‐one ( 8 ), were isolated from the twigs and leaves of Aleurites moluccana. Their structures were elucidated by means of comprehensive spectroscopic analyses, including NMR and MS. Except 8 , all compounds were evaluated for their cytotoxicity; compound 4 exhibited moderate inhibitory activity against Raji cells with an IC₅₀ value of 4.24 μg/ml.     

Synthesis of (E)-8-aza-11-deoxy-15α- and 15β-hydroxyprost-13-en-1-ol

The synthesis of a prostaglandin E₁ analog, (E)-8-aza-11-deoxy-15α- and 15β-hydroxyprost-13-en-1-ol, is reported.     

The Terpenoids of Maytenus boaria MOL. (Celastraceae)

The known triterpenoids β-amyrin (= olean-12-en-3β-ol; 22 ), lupeol (= lup-20(29)-en-3β-ol; 17 ), betulin (= lup-20(29)-ene-3β,28-diol; 18 ), lup-20(29)-ene-3β,30-diol ( 20 ), oleanolic acid (= 3β-hydroxyolean-12-en-28-oic acid; 21 ), and betulonic acid (= 3-oxolup-20(29)-en-28-oic acid; 19 ), together with epicatechol (= cis-2-(3,4-dihydroxyphenyl)-3,4-dihydro-2H-1-benzopyran-3,5,7-triol; 23 ), 5′-O-methylgallocatechol (= trans-2-(3,4-dihydroxy-5-methoxyphenyl)-3,4-dihydro-2H-1-benzopyran-3,5,7-triol; 24 ), and 4-hydroxybenzaldehyde were isolated from the aerial parts of Maytenus boaria (MOL. ). Additonally, the eight 4,C⁴-dihydro-β-agarofuran sesquiterpenoids 1–8 , one of them a diol with a (4R)-configuration, and compound 9 were present in the extract. The structures of these compounds were established by spectroscopic and chemical means.     

Photosensitized Oxygenation of Abieta-7,9(11)-dien-13β-ol

Dehydration of abiet-8-ene-7β, 13β-diol (ibozol, 1 ) leads to abieta-7,9(11)-dien-13β-ol ( 2 ) which aromatizes slowly to the known abieta-8,11,13-triene ( 3 ). Photosensitized oxygenation of the heteroannular diene 2 yields a mixture from which three compounds were identified; abiet-7-ene-9α, 11α, 13β-triol ( 4 ), abieta-8,11,13-trien-7-one ( 5 ), and abieta-8,11,13-trien-7α-ol ( 6 ).     

Identification de stérols à chaînes latérales courtes dans l′éponge Damiriana hawaiiana

Identification of short side chain sterols in the sponge Damiriana hawaiiana The steroidal composition of the sponge Damiriana hawaiiana is examined. Twenty-seven components are identified. In addition to the C₂₆-C₂₉, Δ⁵-mono and diunsaturated sterols, the sponge contains sterols without side-chain: androsta-5, 16-dien-3β-ol( 1 ), androst-5-en-3β-ol( 2 ); sterols with a non-functionalized side-chain consisting of two, three, four, five and six carbon atoms: pregna-5, 20-dien-3β-ol( 5 ), pregn-5-en-3β-ol( 6 ), 23, 24-bisnor-chola-5, 20-dien-3β-ol( 7 ), 23, 24-bisnor-chol-5-en-3β-ol( 8 ), 24-nor-chol-5-en-3β-ol( 10 ), chol-5-en-3β-ol( 11 ), 26, 27-bisnor-cholest-5-en-3β-ol( 12 ), and sterols possessing a short oxygenated side-chain such as 3β-hydroxy-androst-5-en-17-one( 3 ), androst-5-en-3β, 17β-diol( 4 ) and 3β-hydroxy-26, 27-bisnor-22-trans-cholesta-5, 22-dien-24-one( 14 ). The probable biological or dietary origin rather than artifact production of these hitherto undescribed components from marine sources is supported by their relatively high concentration and their relative proportions, both very different from those expected for autoxidation.     

Three New Abietane‐type Diterpenes from the Bark of Cryptomeria japonica

Three new abietane‐type diterpenoids, 7β‐acetoxy‐12‐methoxyabieta‐8,11,13‐triene‐6α,11‐diol ( 1 ), 7α‐acetoxy‐12‐methoxyabieta‐8,11,13‐triene‐6α,11‐diol ( 2 ), and 6α‐acetoxy‐12‐methoxyabieta‐8,11,13‐triene‐7α,11‐diol ( 3 ), as well as two known abietane‐type diterpenoids, 12‐methoxyabieta‐8,11,13‐triene‐6α,7β,11‐triol ( 4 ) and 6α‐acetoxy‐12‐methoxyabieta‐8,11,13‐triene‐7β,11‐diol ( 5 ), were isolated from the MeOH extract of the bark of Cryptomeria japonica. Their structures were determined by analysis of spectroscopic data and comparison of NMR data with those of related metabolites.     

Identification of Twenty-one Novel Constituents of Oriental Tobacco Flavour (Nicotiana tabacumL.) including (E)-3-methyl-non-2-en-4-one,pentadecan-15-olide, 8α, 13:9α, 13-diepoxy-15, 16-dinorlabdane, (Z)-octadec-9-en-18-olide,and (E)-2-ethylidene-6, 10, 14-trimethyl-pentadecanal

Investigation by gas liquid chromatography of a small but organoleptically typical subfraction of Oriental tobacco condensate led to the identification of 47 compounds. Of these 21 have hitherto not been reported as Oriental tobacco constituents, and 14 appear to be novel to all tobacco types. The latter are (E)-3-methyl-non-2-en-4-one ( 1 ), (E)-1-(2, 3, 6-trimethylphenyl)-but-2-en-1-one ( 3 ), pentadecan-15-olide ( 12 ), 8α, 13:9α, 13-diepoxy-15, 16-dinorlabdane ( 17 ), (Z)-octadec-9-en-18-olide ( 18 ), (E)-2-ethylidene-6, 10, 14-trimethylpentadecanal ( 21 ), the norlabdanoids 9 , 10 , 11 , 14 , 15 , 16 , tridecan-2-one, and 2-phenylethyl isovalerate. The macrolides 12 and 18 represent the first musk compounds detected in tobacco. Identification were made by direct comparison (MS. and/or ¹ H-NMR./IR.) with the authentic chemicals synthesized whenever necessary.     

New Triterpenes from the Heartwood of Melaleuca leucadendron L.

Fourteen chemical constituents were isolated from the CHCl₃ soluble portion of the heartwood of Melaleuca leucadendron L. These compounds include β-sitosterol (1) , β-sitostenone (2) , 6-hydroxy-4,6-dimethyl-3-hepten-2-one (3) , naphthalene (4) , squalene (5) , 2α3β-dihydroxyurs-12-en-28-oic acid (6) , 3β-hydroxylup-20(29)-en-27,28-dioic acid (7) , 2α,3β-dihydroxyolean-12-en-28-oic acid (8) , 3β,23-dihydroxyolean-12-en-28-oic acid (9) , 2α,3β,23-trihydroxyolean-12-en-28-oic acid (10) , 3β-trans-p-coumaroyloxy-2α,23-dihydroxyolean-12-en-28-oic acid (11) , and three novel oleanane derivatives 23-trans-p-coumaroyloxy-2α,3β-dihydroxyotean-12-en-28-oic acid (12), 3β-trans-caffeoyloxy-2α,23-dihydroxyolean-12-en-28-oic acid (13) , and its isomer 3β-cis-caffeoyloxy-2α,23-dihydroxyolean-12-en-28-oic acid (14) , The three novel compounds were characterized as the two and three O-methylated derivatives, respectively.     

Microbial hydroxylation and glycosidation of oleanolic acid by Circinella muscae and their anti-inflammatory activities

Biotransformation of oleanolic acid (OA) by Circinella muscae AS 3.2695 was investigated. Nine hydroxylated and glycosylated metabolites (1–9) were obtained. Their structures were elucidated as 3β,7β-dihydroxyolean-12-en-28-oic acid (1), 3β,7β,21β-trihydroxyolean-12-en-28-oic acid (2), 3β,7α,21β-trihydroxyolean-12-en- 28-oic acid (3), 3β,7β,15α-trihydroxyolean-12-en-28-oic acid (4), 7β,15α-dihydroxy- 3-oxo-olean-12-en-28-oic acid (5), 7β-hydroxy-3-oxo-olean-12-en-28-oic acid (6), oleanolic acid-28-O-β-D-glucopyranosyl ester (7), 3β,21β-dihydroxyolean-12-en-28- oic acid-28-O-β-D-glucopyranosyl ester (8), and 3β,7β,15α-trihydroxyolean-12-en- 28-oic acid-28-O-β-D-glucopyranosyl ester (9) by spectroscopic analysis. Among them, compounds 4 and 9 were new compounds. In addition, anti-inflammatory activities were assayed and evaluated for the isolated metabolites. Most of the metabolites exhibited significant inhibitory activities on lipopolysaccharides-induced NO production in RAW 264.7 cells.     

Microbial Metabolism of the Diterpene Sclareol: Oxidation of the A Ring by Septomyxa affinis

Microbial metabolism of the diterpene sclareol ( 1 ) was studied. Screening studies have shown a number of microorganisms capable of metabolizing 1 . Preparative-scale fermentation with Septomyxa affinis ATCC 6737 has resulted in the production of three fungal metabolites that have been characterized by 2D-NMR techniques and chemical reactions. These metabolites have been identified as 8α,13β-dihydroxylabd-14-en-3-one ( 2 ), labd-14-ene-3β.8α,13β-triol ( 4 ), and labd-14-ene-2α,8α,13β-triol ( 6 ).     

New Sesquiterpene Glycosides from Culture Hairy Roots of Catharanthus roseus

Two new compounds cadin-2-en-1β-ol-1β-D-glucuronopyranoside （1）, guaia-l,7-dien-3β,13-diol-13α-D- glucofuranoside （2） along with three known compounds have been isolated from the culture hairy roots of Catharanthus roseus. Their structures have been elucidated with the help of 500 MHz NMR using 1D and 2D spectral methods： viz： ^1H and ^13C NMR, ^1H-^1H COSY, ^1H-^13C HETCOR and DEPT aided by ELMS, FAB-MS, HR-FABMS and IR spectroscopy.     

Application of biosynthetic 13C-enrichment using [1-13C]-, [2-13C]- and [1,2-13C2]-acetate as precursor for 13C NMR spectral assignment of higher plant metabolites. The assignments of some bryonolic acid derivatives

The ¹³C NMR spectra of some derivatives of bryonolic acid (1) (D:C-friedoolean-8-en-3β-ol-29-oic acid) were assigned by means of ¹³C-enrichment, lanthanide-induced shifts (LIS) and comparison of chemical shift data between derivatives. The ¹³C-enriched species of 1, i.e., 1a, 1b and 1c were biosynthesized by Luffa cylindrica (Cucurbitaceae) callus fed with [1-¹³C]-, [2-¹³C]- or [1,2-¹³C₂]-acetate, respectively. Methyl acetylbryonolates 2, 2a, 2b and 2c, methyl bryonolates 3, 3a, 3b and 3c, methyl bryononates 4 and 4a, diacetyl-3β,29-diols (3,29-diacetyl-D:C-friedoolean-8-en-β,29-diol) 5, 5a, 5b and 5c, and 3-acetyl-3β,29-diols 6, 6a and 6b were prepared from 1, 1a, 1b and 1c, and their ¹³C NMR spectra were recorded. The ¹³C concentration of the ¹³C-enriched species was high enough to exhibit the satellite peaks clearly, and the analysed data were very useful for this study. Thus, total assignments for 2, 3, 4, 5 and 6 were established. It was found that conversion of the methoxycarbonyl group at C-29 into an acetoxymethyl group caused complex changes in the chemical shifts of the C, D- and E-ring carbons and those of the methyl carbons linked to these rings.     

Differential-pulse polarography of trichothecene mycotoxins : Determination of Deoxynivalenol,Nivalenol and Fusarenone-X in Maize

The polarographic behaviour of representative trichothecenes is described. Compounds characterized by an α,β-unsaturated carbonyl group or by a macrocyclic lactonic ring were found to be electroactive in a methanolic Britton—Robinson buffer. Differential pulse polarography provides detection limits of the order of 40 nmol l^?1 with linear ranges extending up to 9 μmol l^?1. The application of differential pulse polarography is described for the determination of nivalenol (3α, 4β, 7α, 15-tetrahydroxy-12,13-epoxytrichotec-9-en-8-one), deoxynivalenol (3α, 7α, 15-trihydroxy-12,13-epoxytrichothec-9-en-8-one) and fusarenone-X (3α, 7α, 15-trihydroxy-4 β-acetoxy-12,13-epoxytrichothec-9-en-8-one) in infected maize. A suitable liquid/liquid extraction and chromatographic cleanup procedure is reported. Detection limits for the overall procedure and for a sample size of 50 g are of the order of 50 ng g^?1 while average recoveries range from 20 to 70% at the 1 μg g^?1 level. Polarographic results are compared with those obtained by a gas-chromatographic method.     

华泽兰的七个新的倍半萜

Seven new sesquiterpenoids, namely eupatochinilides Ⅰ-Ⅶ （1-7）, together with eight known compounds, euponin （8）, mollisorin A （9）, niveusin B （10）, 8β-（4＇-acetoxy-tiglyloxy）-3β-hydroxy-6Hβ,7Hα-germacra-1（10）E,4E,11（13）-trien-6,12-olide （11）, eupalinifide B （12）, 8β-（4＇-hydroxytigloyloxy）-5-desoxy-8-desacyleuparotin （13）, 3-deacetyeupalinin A （14）, and 15-hydroxyleptocarpin （15）, were isolated from the ethanolic extract of the whole plant of Eupatorium chinense L. Their structures and stereochemistry were established by spectroscopic methods and GIAO based ^13C NMR chemical shift calculations.     

Synthesis of 3β-Hydroxy[21-14C]-5β-pregn-8(14)-en-20-one from Chenodeoxycholic Acid

3β-Hydroxy[21-¹⁴C]5β-pregn-8(14)-en-20-one ( 17 ) was prepared from chenodeoxycholic acid ( 1a ). The synthetic sequence involved: (i) degradation of the bile-acid side chain to an etianic acid; (ii) formation of the 8(14)-double bond; (iii) inversion of the configuration at C(3); (iv) construction of the acetyl side chain at C(17) with the required isotopic label at C(21). Structures of all described products were confirmed by chemical and spectroscopic (IR, ¹H-NMR, ¹³C-NMR, MS) methods.     

Constituents of Fruit Bodies of Tramete orientalis

A known sterol, 5α,6α-epoxy-5α-crgosta-8(14),22E-diene-3β,7α-diol ( 1 ), and two new sterols, 5α,6α-epoxy-3β,8β,14α-trihydroxy-5α-ergost-22E-en-7-one ( 2 ), (3α,5α),(8β,11β)-diepidioxy-ergost-22E-en-12-one ( 3 ), were isolated and characterized from dried fruit bodies of Trametes orientalis. Their structures were elucidated according to spectral methods.     

ENANTIOSELECTIVE TOTAL SYNTHESES OF 13-ACETYL- 12-HYDROXY-PODOCARPANE- 8,11,13-TRIENE-7-ONE

ABSTRACT

A enantioselective total synthetic route to (+)-13-acteyl-12-hydroxy-podocarpane-8,11,13-triene-7-one 1a and (?)-13-acetyl-12-hydroxy-podocarpane-8,11,13-triene-7-one 1b from (S)-(?)-α-cyclocitral 8a and (R)-(+)-α-cyclocitral 8b was developed.     

大叶橐吾中三个新的艾里莫芬型倍半萜

从大叶橐吾的根部分离得到三个新的艾里莫芬型倍半萜(1, 2和3), 经多种波谱方法和单晶X射线衍射确定它们的结构分别为: 6α,15β-环氧-8β-羟基-艾里莫芬-7(11)-烯-8α,12-内酯(1), 7-乙酰基-13β-羧酸-6(7)-烯-降-艾里莫芬烷(2), 艾里莫芬-7(11)-烯-6α,15β-内酯(3). 此外, 对化合物1进行了抗菌和抗癌活性测试.     

Two New Lycopodine Alkaloids from Huperzia serrata

Two new lycopodine alkaloids, (12β)‐12‐hydroxyhuperzine G ( 1 ) and (5β,6β,15α)‐15‐methyllycopodane‐5,6‐diol ( 2 ), were isolated from the whole plants of Huperzia serrata, together with six known compounds, huperzines A, B, and G, phlegmariurine B, (8β)‐8‐hydroxyphlegmariurine B, and lycoposerramine D. Their structures were elucidated on the basis of spectroscopic analysis, including HR‐ESI‐MS, ¹H‐ and ¹³C‐NMR, DEPT, ¹H,¹H‐COSY, HSQC, HMBC, and NOESY data.     

Novel Sesquiterpenoids from Siegesbeckia orientalis

Five new sesquiterpenoids, namely, 8β‐(angeloyloxy)‐4β,6α,15‐trihydroxy‐14‐oxoguaia‐9,11(13)‐dien‐12‐oic acid 12,6‐lactone ( 1 ), 4β,6α,15‐trihydroxy‐8β‐(isobutyryloxy)‐14‐oxoguaia‐9,11(13)‐dien‐12‐oic acid 12,6‐lactone ( 2 ), 11,12,13‐trinorguai‐6‐ene‐4β,10β‐diol ( 3 ), (1(10)E,4E,8Z)‐8‐(angeloyloxy)‐6α,15‐dihydroxy‐14‐oxogermacra‐(1(10),4,8,11(13)‐tetraen‐12‐oic acid 12,6‐lactone ( 9 ), and (1(10)E,4β)‐8β‐(angeloyloxy)‐6α,14,15‐trihydroxygermacra‐1(10),11(13)‐dien‐12‐oic acid 12,6‐lactone ( 11 ), and three new artifacts, (1(10)E,4Z)‐8β‐(angeloyloxy)‐9α‐ethoxy‐6α,15‐dihydroxy‐14‐oxogermacra‐1(10),4,11(13)‐trien‐12‐oic acid 12,6‐lactone ( 6 ), (1(10)E,4Z)‐8β‐(angeloyloxy)‐9α,13‐diethoxy‐6α,15‐dihydroxy‐14‐oxogermacra‐1(10),4‐dien‐12‐oic acid 12,6‐lactone ( 7 ), and (1(10)E,4Z)‐8β‐(angeloyloxy)‐9α‐ethoxy‐6α,15‐dihydroxy‐13‐methoxy‐14‐oxogermacra‐1(10),4‐dien‐12‐oic acid 12,6‐lactone ( 8 ), together with the three known sesquiterpenoids 4, 5 , and 10 , were isolated from the aerial parts of Siegesbeckia orientalis L. Their structures were established by spectral methods, especially 1D‐ and 2D‐NMR spectral methods.