Triterpenoids from Abies species X. Two new 3,4-secotriterpene acids from the oleoresin of the silver fir

Two new 3,4-secotriterpene acids have been isolated in the form of dimethyl esters from the acid fraction of the oleoresin of the silver firAbies alba Mill. On the basis of spectral characteristics and the results of a chemical correlation with the known triterpenoids methyl abiesolidate, dimethyl abiesonate and methyl firmanoate it has been established that they are (25R)-3,4-seco-9-lanosta-4(28),7-dien-23-one-3,26-dioic acid and (25R)-3,4-seco-abiesa-4(28),7,14(30)-trien-23-one-3,26-dioic acid.Institute of Organic Chemistry, Siberian Branch, Academy of Sciences of the USSR, Novosibirsk. Translated from Khimiya Prirodnykh Soedinenii, No. 6, pp. 765–770, November–December, 1990.     

A new 3,4-seco-cycloartane from the leaves of Hopea odorata Roxb.

A new 3,4-seco-cycloartane, identified as (24R,25S)-dihydroxy-26-O-nonadecylcarbonyloxy-3,4-secocycloarta-4(28)-en-3-oic acid (1), has been isolated from the leaves of Hopea odorata Roxb. (Dipterocarpaceae), together with the rare 3,4-seco-cycloart-4(28),24-diene-3,26-dioic acid (2 or abiesatrine J) and six other known compounds (3–8). Their structures were elucidated on the basis of both chemical and spectroscopic methods.     

Condensed heterotricycles: Pyrido(1,2,3- de )(1,4)benzoxazines, pyrido(1,2,3- ef )(1,5)benzoxazepines and pyrido(1,2,3- fg )(1,6) benzoxazocines

Cyclization of N-(2-haloacyl)-8-hydroxy-l,2,3,4-tetrahydroqumolines4–7 and9 with alkali affords pyridobenzoxazinones21–24 and26 respectively and of the 4-chlorobutyramide13 with NaH, the benzoxazocinone31. Exposure of 3-chloropropionamide12 to NaH affords acrylamide15, benzoxazepinone28 or methyl benzoxazinone22 or mixtures thereof under various conditions.28 undergoes rapid base-catalysed ring contraction to22. NaH-catalysed ring closure of acrylamide15 affords mixtures of22 and28, while from the crotonamides16 and17, the methylbenzoxazepinones29 and30 are obtained preponderantly, the former amide yielding only traces of the ethyl benzoxazinone23.29 shows no propensity for ring contraction to give23. The cinnamoyl derivatives18,19 and20 are cyclized to benzyl benzoxazinones24,27 and25, respectively. The intermediacy of the phenyl benzoxazepinone39 in the formation of24 has been established by deuteration studies. Benzylidene benzoxazinone41 is obtained from dibromocinnamamide14 and propiolamide40. Dichloracetamides8 and10 undergo interesting ring closure to compounds45–54 upon treatment with amines. The course of electrophilic reactions of the lactams depends upon the ring size. Contribution No. 18 from Searle R & D Centre Presented at a symposium to felicitate Prof N S Narasimhan at the University of Poona, November 18–19, 1988     

Chemoselective oxidation of oleanolic acid derivatives with ozone

A method for preparing methyl esters of 12-oxoolean-28-oic and 3,12-dioxoolean-28-oic acids via ozonolysis of oleanolic acid methyl ester in CH₂Cl₂ at –60°C was proposed. It was found that oxidation of 2-cyano3,4-seco-4(23)-oleanenoic acid was chemoselective depending on the amount of ozone used.     

Triterpenoids from species ofAbies hill. II. Abiesolidic acid — A new 3,4-secolanostanoid from the oleoresin ofAbies sibirica

The oleoresin of the Siberian fir has yielded a new 3,4-secolanostanoid for which the structure of (20R,23S,25R)-3,4-seco-9β-lanosta-4(28),7-dien-26,23-olid-3-oic acid has been established by x-ray structural analysis. The pathways of the mass-spectrometric fragmentation of this acid and its esters have been investigated.     

Triterpene glycosides of Astragalus and their genins XXXIX. Cycloaraloside D from Astragalus amarus

The structure of a triterpene glycoside of the cycloartane series — cycloaraloside D, isolated from the roots ofAstragalus amarus Pall. (Leguminosae) — has been established on the basis of chemical transformations and spectral characteristics. Cycloaraloside D is 20R, 24S-epoxycycloartane-3β, 6α, 16β, 25-tetraol 3-0-[0-α-L-rhamnopyranosyl-(1 → 2)-β-D-glucopyranoside]. Institute of Chemistry of Plant Substances, Academy of Sciences of the Uzbek SSR, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 4, pp. 526–528, July–August, 1991.     

Two new echinocystic acid derivatives catalyzed by filamentous fungus Gliocladium roseum CGMCC 3.3657

Biotransformation of Echinocystic acid (EA,1) using G. roseum CGMCC 3.3657 has been investigated, which leads to the isolation and identification of two novel Echinocystic acid derivatives, 4, 16α-dihydroxy-3,4-seco-olean-12-en-3,28-dioic acid (2) and 16α-hydroxy, A-homo-3α-oxa-olean-12-en-3-one-28-oic acid (3). Their structures have been elucidated by analysis of spectroscopic data. This biocatalysis could serve as an efficient tool complementary to classical chemical methods for the transformation of EA.     

New oleanene glycosides from the leaves of Acanthopanax japonicus

The structures of 6 new oleanene glycosides (1--6) isolated from the leaves of Acanthopanax japonicus FRANCH et. SAVART (Araliaceae) were elucidated by mass, 1D, and 2D NMR spectroscopy. The structures of 1--6 were established as 28-O-[alpha-L-rhamnopyranosyl-(1-->4)-beta-D-glucopyranosyl-(1-->6)-beta-D-glucopyranosyl] ester of 3beta,23-dihydroxy-olean-12-en-28,29-dioic acid, 3beta,30-dihydroxy-olean-12-en-23,28-dioic acid, 3beta,29-dihydroxy-olean-12-en-23,28-dioic acid (=dianic aicd), 3beta-dihydroxy-olean-12-en-23,28-dioic acid (=gypsogenic acid), 3beta,29-dihydroxy-23-oxo-olean-12-en-28-oic acid, and 3beta-hydroxy-23-oxo-olean-12-en-28,29-dioic acid, designated acanjaposide D (1), E (2), F (3), G (4), H (5), and I (6), respectively.     

Steroids of the spirostan and furostan series from plants of the genus Allium. XXVI. Structure of anzurogenin and anzuroside from the collective fruits of Allium suvorovii and Allium stipitatum

A new steroid glycoside of the spirostan series, anzuroside, has been isolated from the collective fruits of the cocultivatedAllium suvorovii Rgl. andA. stipitatum Rgl. (family Liliaceae, local name “anzur”). Enzymatic cleavage of the glycoside has given the previously undescribed steroid sapogenin anzurogenic C, which has the structure of (24S, 25S)-2α,3β,5,24-tetrahydroxy-5β-spirostan-6-one. Anzuroside is the 24-O-β-D-glucopyranoside of anzurogenin C. Institute of the Chemistry of Plant Substances, Uzbek SSR Academy of Sciences, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 4, pp. 505–510, July–August, 1989.     

Brugnanin,a new syn-2,3-dihydrobenzofuran neolignan dioate from the mangrove <Emphasis Type="Italic">Bruguiera gymnorrhiza</Emphasis>

Brugnanin (1), a neolignan dioate, was isolated from a mangrove plant Bruguiera gymnorrhiza. Based on spectroscopic interpretation of MS, IR, and NMR data, 1 was elucidated as (7R*,8S*,E)-3-hydroxy-5,5′-dimethoxy-7-O-4′,8-3′-neolignan-7′-ene-9,9′-dioic acid dioctadecyl ester. MTT assay showed that 1 had weak inhibitory activity against growth of CNE-1 nasopharyngeal carcinoma cell line. Published in Khimiya Prirodnykh Soedinenii, No. 2, pp. 147–149, March–April, 2008.     

Insect pheromones and their analogues XLIII. Chiral pheromones from (S)-(+)-3,7-dimethylocta-1,6-diene 3. Synthesis of (4R)-4-methylnonan-1-OL — Sex pheromone of Tenebrio molitor and its racemic analogue

Starting from the readily available enantiomerically enriched (S)-(+)-3,7-dimethylocta-1,6-diene (ee ≃ 50%), we have synthesized (4R)-4-methylnonan-1-ol — the sex pheromone of the yellow mealworm bettleTenebrio molitor L. A scheme for synthesizing the racemic analogue of the pheromone from 4-methyltetrahydropyran has been developed. Institute of Organic Chemistry, Urals Branch, Russian Academy of Sciences. Translated from Khimiya Prirodnykh Soedinenii, No. 6, pp. 711–714, November–December, 1992.     

Triterpene glycosides of Astragalus and their genins XXXV. Cycloaraloside C from Astragalus amarus

A new triterpene glycoside of the cycloartane series (cycloaraloside C) has been isolated from the roots of the plantAstragalus amarus Pall. (Leguminosae). Cycloaraloside C is a bioside of cyclosieversigenin including one D-glucose residue and one D-apiose residue. The structure of the glycoside has been shown on the basis of the chemical transformations and spectral characteristics as 20R,24S-epoxycycloartane-3β,6α,16β,25-tetraol 3-O-[O-(D-apio-β-D-furanosyl)-(1 → 2)-β-D-glucopyranoside]. This is the first time that D-apiose has been found among cycloartane glycosides. Institute of Chemistry of Plant Substances, Academy of Sciences of the Uzbek, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 6, pp. 783–787, November–December, 1990.     

Lupane glycosides from the leaves of Acanthopanax koreanum

Three new lupane-type saponins, acankoreosides F--H (1--3) were isolated from the methanol extract of the leaves of Acanthopanax koreanum NAKAI. The structures of these three saponins were established by chemical and spectroscopic analysis as 3alpha,30-dihydroxylup-20(29)-en-23,28-dioic acid 28-O-[alpha-L-rhamnopyranosyl-(1-->4)-beta-D-glucopyranosyl-(1-->6)-beta-D-glucopyranosyl] ester (1), 3alpha,30-dihydroxylup-23-al-20(29)-en-28-oic acid 28-O-[alpha-L-rhamnopyranosyl-(1-->4)-beta-D-glucopyranosyl-(1-->6)-beta-D-glucopyranosyl] ester (2), and (20S) 3alpha-hydroxylup-23-al-28,29-dioic acid 28-O-[alpha-L-rhamnopyranosyl-(1-->4)-beta-D-glucopyranosyl-(1-->6)-beta-D-glucopyranosyl] ester (3), respectively. The effects of the isolates (1-3) on the lipopolysaccharide-induced production of nitric oxide and prostaglandin E2 were evaluated in RAW 264.7 macrophages.     

Triterpene glycosides of Astragalus and their genins XXXII. Cyclocarposide from Astragalus coluteocarpus

A new triterpene glycoside of the cycloartane series, which has been called cyclocarposide, has been isolated from the epigeal part of the plantAstragalus coluteocarpus Boiss. (Leguminosae). The structure of cyclocarposide has been established on the basis of chemical transformations and spectral characteristics as 20R,24S-epoxycycloartane-3β,6α,16β,25-tetraol 6-0-α-L-rhamnopyranoside 3-0-α-D-xylopyranoside. Institute of Chemistry of Plant Substances, Academy of Sciences of the Uzbek SSR, Tashkent. Pamir Biological Institute, Academy of Sciences of the Tadzhik SSR, Khorog. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 653–656, September–October, 1990.     

Novel A-seco-rearranged lanostane triterpenoids from Abies sachalinensis

From the needles of Abies sachalinensis, novel rearranged lanostane type triterpenes, 1-4, were isolated along with a known triterpene (5). The structures of the new compounds, 1-4, were elucidated to be 3,4-seco-8-(14-->13R)abeo-17,13-friedo-9beta-lanosta-4(28),7,14(30),22Z,24-pentaen-26,23-olide-3-oic acid, methyl 3,4-seco-8-(14-->13R)abeo-17,13-friedo-9beta-lanosta-4(28),7,14(30),22Z,24-penten-26,23-olide-3-oate, 3,4-seco-8(14-->13R)abeo-17,13-friedo-9beta-lanosta-4(28),7,14,22Z,24-pentaene-26,23-olide-3-oic acid and methyl 3,4-seco-8(14-->13R)abeo-17,13-friedo-9beta-lanosta-4(28),7,14,22Z,24-pentaene-26,23-olide-3-oate, respectively, by means of spectral experiments, especially two dimensional NMR spectroscopy, such as 1H-detected multiple quantum coherence (HMQC), 1H-detected heteronuclear multiple bond connectivity (HMBC) and 1H-1H-correlation spectroscopy (COSY) experiments. These new compounds have novel structures containing A-seco, rearranged spiro structure and a gamma-lactone conjugated with a diene. Some of these compounds showed potent antibacterial activity against gram positive bacteria.     

Stereoselective synthesis of highly enantioenriched 3-methyl-2-cyclohexen-1-ones possessing an asymmetric quaternary carbon as C-4 or C-6: a sugar template approach

The 1,4-addition of the enolate generated from α-methylated acetoacetate incorporated at C-4 of methyl 6-deoxy-2,3-di-O-(tert-butyldimethylsilyl)-α-d-glucopyranoside to methyl vinyl ketone, followed by aldol condensation of the resulting 1,4-addition product under two base-mediated conditions, provided 4-O-functionalized d-glucose derivatives with high diastereoselectivity. These products install a 3-methyl-2-cyclohexen-1-one-4- (or -6-) carboxylic acid as the O-4 ester, in which C-4 or C-6 is an asymmetric quaternary carbon. Removal of the sugar template from those aldol condensation products provided synthetically useful 3,6-dimethyl-2-cyclohexen-1-one-6-carboxylic acid and 3,4-dimethyl-2-cyclohexen-1-one-4-carboxylic acid derivatives both in high enantioenriched forms.     

Triterpene glycosides of Thalictrum squarrosum. IV. Structures of squarrosides A1, A2, B1, and B2

Four new cycloartane glycosides have been isolated from a methanolic extract ofThalictrum squarrosum Stephan ex Willd.: squarroside A1 (I) — (21R, 22S, 23R)-3β-(β-D-glucopyranosyloxy)-21α-methoxy-21,23-epoxycycloart-24-ene-22β,30-diol, C₃₀H₆₀O₁₀; squarroside A2 (II) — the (21S)-epimer of compound (I); squarroside B1 (III) (21R, 22S, 23R)-3gb-[O-α-L-rhamnopyranosyl-(1 → 6)-β-D-glucopyranosyloxy]-21α-methoxy-21,23-epoxycycloart-24-ene-22β,30-diol, C₄₃H₇₀O₁₄; and squarroside B2 (IV) — the (21S)-epimer of compound (III). The proposed structures were determined on the basis of¹H and¹³C NMR spectroscopy, FAB mass spectrometry, and chemical transformations. Irkutsk Institute of Organic Chemistry, Siberian Branch, USSR Academy of Sciences. Translated from Khimiya Prirodnykh Soedinenii, No. 4, pp. 516–523, July–August, 1989.     

New steroidal sapogenins from the acid hydrolysis product of the whole glycoside mixture of Welsh onion seeds

Two new steroidal sapogenins(1,2) along with five known steroidal sapogenins were isolated from the acid hydrolysis product of the whole glycoside mixture of Welsh onion(Allium fistulosum L.) seeds.Based on comprehensive spectroscopic analyses, including 2D NMR spectroscopy and mass spectrometry,their structures were elucidated as(25R)-19-norspirosta-l,3,5(10)-triene-4 -methyl-2-ol(1),(25R)-spirost-l,4-diene-3-one-2,6-diol(2),(25R)-spirost-l,4-diene-3-one-2-ol(3),(25R)-spirost-4-ene-3-one-2-ol (4),yuccagenin(5),gitogenin(6) and tigogenin(7).     

Steroids of the spirostan and furostan series from nolina microcarpa III. Structure of nolinofurosides G and H

Two new glycosides which have been called nolinofurosides G(I) and H(III), have been isolated from the leaves ofNolina microcarpa. Nolinofuroside G is the sodium salt of 26-β-D-glucofuranosyloxy-(25S)-furost-5,20(22)-diene-1β, 3β-diol 1-sulfate, and nolinofuroside H is the sodium salt of 1-β-D-fucopyranosyloxy-26-β-D-glucopyranosyloxy-(25S)-furost-5,20(22)-dinen-1β-3β-ol 3-sulfate. M. V. Frunze Simferopol' State University. Institute of the Chemistry of Plant Substances, Uzbek. Academy of Sciences, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 6, pp. 801–806, November–December, 1991.     

Cytotoxic lupane-, secolupane-, and oleanane-type triterpenes from Viburnum awabuki

Bioassay-guided fractionation of the methanolic extract of Viburnum awabuki afforded two new lupane triterpene derivatives; 6 beta-hydroxyl-3,20-dioxo-30 norlupane-28-oic acid (1) and 3,4-secolup-4,20-dihydroxy-3,28-dioic acid-3-oic acid methyl ester (2), along with seven known lupane and oleanane-type triterpenes (3-9). The structure of the isolated compounds was assigned using different spectroscopic techniques including 1D and 2D NMR. The 13CNMR data of compounds 5 and 9 is reported for the first time. Triterpenes 1, 2, and 7-9 showed in vitro cytotoxic activity against several tumor cell lines.