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.     

Terpenes in organic synthesis. 7. Synthesis of (S)-(+)-3-methylheneicosan-2-one from (s)-(+)-3,7-dimethylocta-1,6-diene

Conclusions From (S)-(+)-3,7-dimethylocta-1,6-diene there has been synthesized (S)-(+)-3-methyl-heneicosan-2-one, a biologically active analog of the sex pheromone of the German cockroachBlatella germanica.For previous communication, see [1].Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 3, pp. 693–695, March, 1988.     

Oxidation studies on some natural monoterpenes: Citral, pulegone, and camphene

Citral extracted from Cymbopogon citratus (Gramineae) was subjected to photochemical epoxidation with hydrogen peroxide to obtain a mixture of epoxy derivatives at the C²=C³ and C⁶=C⁷ double bonds. The thermal oxidation of citral with m-chloroperoxybenzoic acid at room temperature gave only the corresponding 6,7-epoxy derivative as a mixture of E and Z isomers with respect to the C²=C³ double bond. Photosensitized oxygenation of citral in the presence of tetraphenylporphyrin, Rose Bengal, or chlorophyll lead to a mixture of two isomeric hydroperoxides, (2E)-6-hydroperoxy-3,7-dimethylocta-2,7-dienal and (2E,5E)-7-hydroperoxy-3,7-dimethylocta-2,5-dienal. Epoxidation of pulegone isolated from Penny royal oil (Mentha pulegium, Lamiaceae) with hydrogen peroxide under irradiation with a sodium lamp lead to a mixture of cis- and trans-isomeric 2,2,6-trimethyl-1-oxaspiro[2.5]octan-4-ones, whereas under conditions of photosensitized oxygenation two hydroperoxide derivatives, 2-(1-hydroperoxy-1-methylethyl)-5-methylcyclohex-2-en-1-one and 2-hydroperoxy-5-methyl-2-(1-methylethenyl)cyclohexan-1-one, were also formed. Camphene reacted with hydrogen peroxide under irradiation to give a mixture of the corresponding endo- and exo-epoxy derivatives and camphor, while its thermal oxidation with m-chloroperoxybenzoic produced only the two former. Published in Russian in Zhurnal Organicheskoi Khimii, 2008, Vol. 44, No. 6, pp. 825–833. The text was submitted by the authors in English.     

Studies related to carba-pyranoses: a radical decarboxylation approach to monocarba-disaccharides

(1--> 1), (1--> 3) and (1--> 4) acetal-linked monocarba-disaccharides have been synthesised from a series of glucosylated gamma- and delta-lactonic acids prepared from common intermediate, obtained from the Diels-Alder reaction of maleic anhydride and (E)-1-(2',3',4',6'-tetra-O-acetyl-beta-D-glucopyranosyloxy)-3-(trimethylsiloxy)buta-1,3-diene 1. Thiohydroxamic ester 14, prepared from gamma-lactonic acid 9, gave, upon treatment with tert-butyl thiol and light, the lactone 15. Subsequent lithium aluminium hydride reduction and acetylation gave the (1--> 3) acetal-linked monocarbadisaccharides 1,6-di-O-acetyl-3-O-(2',3',4',6'-tetra-O-acetyl-beta-D-glucopyranosyl)-2,4-dideoxy-5a-carba-beta-L-threo-hexopyranose 16. In a similar manner, protected monocarba-disaccharides 13, 19, 30, and 35 possessing L-ido, L-xylo, D-arabino and L-ido configurations of the carba-pyranose ring have been prepared. Treatment of thiohydroxamic esters 14 and 17 with either tert-butyl thiol or trityl thiol, dimethyl sulfide, oxygen and light gave alcohols 20 and 22. Subsequent lithium aluminium hydride reduction and aceytlation gave the monocarbadisaccharides 1,4,6-tri-O-acetyl-3-O-[2',3',4',6'-tetra-O-acetyl-beta-D-glucopyranosyl]-2-deoxy-5a-carba-beta-L-arabino-hexopyranose 21 and 1,2,4,6-tetra-O-acetyl-3-O-(2',3',4',6'-tetra-O-acetyl-beta-D-glucopyranosyl)-5a-carba-beta-L-glucopyranose 23 respectively.     

Terpenes in organic synthesis. 6. Synthesis of (R)-(−)-10-methyldodecyl acetate from (S)-(+)-3,7-dimethylocta-1,6-diene

Conclusions (R)-(–)-10-Methyldodecyl acetate, a biospecific minor component of the sex pheromone of the small tea tortrix moth, has been synthesized from the readily accessible compounds (S)-(+)-3,7-dimethylocta-1,6-diene and acrolein.For previous communication, see [1].Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 3, pp. 690–693, March, 1988.     

Cytotoxic and antimicrobial aporphine alkaloids from Fissistigma poilanei (Annonaceae) collected in Vietnam

Two new aporphine alkaloids: 8-hydroxy-9-methoxy-1,2-methylenedioxyaporphine (1) and 8-hydroxy-3,9-dimethoxy-1,2-methylenedioxyaporphine (2) were isolated from the ethyl acetate extract of Fissistigma poilanei along with five known compounds: oxocrebanine (3), kuafumine (4), (2R,3R)-3',4',5,7-tetrahydroxydihydroflavonol-3-O-α-L-rhamnopyranoside (5), (+)-catechin 3-O-α-L-rhamnopyranoside (6) and quercetine 3,7-dimethoxy-3'-O-α-L-rhamnopyranosyl-(1?→?2)-β-D-glucopyranoside (7). These two new aporphine alkaloids exhibited a moderate cytotoxic activity against four human cancer cell lines (KB, Hep-G2, MCF-7, LU) as well as antimicrobial activity against Lactobacillus fermentum, Enterococcus faecium, Staphylococcus aureus and Bacillus subtillis.     

New phenolic principles from Hypericum sampsonii

Using the anti-hepatitis B virus (HBV)-producing cell line MS-G2 in vitro cultural system-guided screening was performed, and two new benzophenones, 2,6-dihydroxy-4-[(E)-5-hydroxy-3,7-dimethylocta-2,7-dienyloxy]benzophenone (1) and 2,6-dihydroxy-4-[(E)-7-hydroxy-3,7-dimethylocta-2-enyloxy]benzophenone (2), a new xanthone, hyperxanthone (3), a new bisanthraquinone glycoside, R-(-)-skyrin-6-O-beta-D-xylopyranoside (4), and 2-caffeoyloxy-3-hydroxy-3-(3,4-dihydroxyphenyl)propyl alcohol (5), and 16 known compounds were isolated from the anti-HBV active fraction of the whole herbs of Hypericum sampsonii. Their structures were elucidated using spectroscopic methods, mainly 2D NMR and MS spectrometry. Circular dichroism was used to determine the stereochemistry of bisanthraquinone glycosides.     

Terpenoids of the rhizomes ofRhodiola rosea

The structures of two new monoterpene compounds isolated from the rhizomes ofRhodiola rosea L. (Crassulaceae) have been established: 3,7-dimethylocta-2,6-diene-1,4-diol (rosiridol) and 3,7-dimethylocta-2,6-diene-1,4-diol 1-O-β-D-glucopyranoside (rosiridin). Daucosterol has been isolated from the rhizomes of this plant for the first time.     

Superacidic cyclization of ω-hydroxygeraniol diacetate and ω-hydroxygeraniol benzyl ether acetate

Low-temperature superacidic cyclization of (E,E)-3,7-dimethylocta-2,6-diene-1,8-diol (ω-hydroxygeraniol) diacetate and (E,E)-8-acetoxy-1-benzyloxy-3,7-dimethylocta-2,6-diene leads to the same mixtures of two diastereomeric 9-acetoxy-8-hydroxy-p-menth-1-enes epimeric at the C(8) atom. Translated fromIzvestiya Akademii Nauk Seriya Khimicheskaya, No. 1, pp. 135–138, January, 1999.     

A new abietane and two dimeric abietane diterpenes from the black heartwood of Cryptomeria japonica

Three new diterpenes, sugikurojins A-C (1-3) were isolated from the black heartwood of Cryptomeria japonica. The structure of sugikurojin A was deduced to be 19-hydroxy-6,7-dehydroferruginol on the basis of extensive NMR experiments. Sugikurojin B was a dimer of 6,7-dihydroxyferruginol and 6,7-dehydroferruginol with a 6-O-11' linkage. Sugikurojin C was a dimeric ferruginol with 6-O-7' and 7-O-6' linkages. Also obtained in this investigation were the known compounds formosaninol (4), 15 sesquiterpenes (5-19), 16 diterpenes (20-35), three phenylpropanoids (36-38), and a phenolic compound (39).     

Phenolic glycosides from Pyrola japonica

Five new phenolic glycosides, 2-beta-D-glucopyranosyloxy-5-hydroxyphenylacetic acid methyl ester (4), 4-hydroxy-2-[3-hydroxy-3-methylbutyl]-5-methylphenyl beta-D-glucopyranoside (5), 4-hydroxy-2-[(E)-4-hydroxy-3-methyl-2-butenyl]-5-methylphenyl beta-D-glucopyranoside (7), 4-hydroxy-2-[(2E,6Z)-8-beta-D-glucopyranosyloxy-3,7-dimethylocta-2,6-dien-1-yl]-5-methylphenyl beta-D-glucopyranoside (8), and 2,7-dimethyl-1,4-dihydronaphthalene-5,8-diol 5-O-beta-D-xylopyranosyl(1-->6)-beta-D-glucopyranoside (10), were isolated from the whole plants of Pyrola japonica (Pyrolaceae), together with androsin, (-)-syringaresinol glucoside, homoarbutin, pirolatin, hyperin, monotropein and chimaphilin.     

Three new glycolipids with cytolytic activity from cultured marine dinoflagellate Heterocapsa circularisquama

A monogalactosyl monoacylglycerol 1 and two digalactosyl monoacylglycerols 2 and 3 were isolated from a cultured marine dinoflagellate Heterocapsa circularisquama along with known (2S)-1-O-6,9,12,15-octadecatetraenoyl-3-O-beta-D-galactopyranosyl]-sn-glycerol (4). On the basis of spectral analysis, the glycolipid 1 was characterised as (2S)-1-O-3,6,9,12,15-octadecapentaenoyl-3-O-beta-D-galactopyranosyl]-sn-glycerol. The glycolipids 2 and 3 were characterised as (2S)-1-O-3,6,9,12,15-octadecapentaenoyl-3-O-[alpha-D-galactopyranosyl-(1' --> 6')-O-beta-D-galactopyranosyl]-sn-glycerol and (2S)-1-O-6,9,12,15-octadecatetraenoyl-3-O-[alpha-D-galactopyranosyl-(1' --> 6')-O-beta-D-galactopyranosyl]-sn-glycerol, respectively. The isolated monoacylglycerols 1-4 showed cytolytic activity towards heart and gill cells of oyster.     

Fortuneanosides G-L, dibenzofuran glycosides from the fruit of Pyracantha fortuneana

Six new dibenzofuran glycosides, fortuneanosides G (1), H (2), I (3), J (4), K (5), and L (6), were isolated from the fruit of Pyracantha fortuneana (MAXIM) LI. Their structures were determined to be 3,7-dihydroxy-2,4-dimethoxy-dibenzofuran 7-O-beta-D-glucopyranoside, 3,7-dihydroxy-2,4-dimethoxy-dibenzofuran 7-O-(alpha-L-rhamnopyranosyl)-(1-6)-beta-D-glucopyranoside, 3,6-dihydroxy-2,4-dimethoxy-dibenzofuran 6-O-beta-D-glucopyranoside, 2,4-dimethoxy-3,6,9-trihydroxy-dibenzofuran 6-O-beta-D-glucopyranoside, 3,9-dihydroxy-2,4-dimethoxy-dibenzofuran 3-O-beta-D-glucopyranoside, and 2-methoxy-3,4,9-trihydroxy-dibenzofuran 4-O-beta-D-glucopyranoside based on spectroscopic analysis. Fortuneanosides G-J showed more potent tyrosinase-inhibitory activity than arbutin.     

Three new flavonoid glycosides, byzantionoside B 6'-O-sulfate and xyloglucoside of (Z)-hex-3-en-1-ol from Ruellia patula

Three new flavonoid glycosides, demethoxycentaureidin 7-O-β-D-galacturonopyranoside, pectolinarigenin 7-O-α-L-rhamnopyranosyl-(1?→4″)-β-D-glucopyranoside and 7-O-α-L-rhamnopyranosyl-(1?→4″)-β-D-glucuronopyranoside, a new megastigmane glucoside, byzantionoside B 6'-O-sulfate, and a new (Z)-hex-3-en-1-ol O-β-D-xylopyranosyl-(1″→2')-β-D-glucopyranoside, were isolated from leaves of Ruellia patula JACQ., together with 12 known compounds, β-sitosterol glucoside, vanilloside, bioside (decaffeoyl verbascoside), acteoside (verbascoside), syringin, benzyl alcohol O-β-D-xylopyranosyl-(1″→2')-β-D-glucopyranoside, cistanoside E, roseoside, phenethyl alcohol O-β-D-xylopyranosyl-(1″→2')-β-D-glucopyranoside, (+)-lyoniresinol 3α-O-β-D-glucopyranoside, isoacteoside and 3,4,5-trimethoxyphenol O-α-L-rhamnopyranosyl-(1″→6')-β-D-glucopyranoside. Their structures were elucidated by means of spectroscopic analyses.     

Bioconversion of 7-Hydroxyflavanone: Isolation, Characterization and Bioactivity Evaluation of Twenty-One Phase I and Phase II Microbial Metabolites

Microbial metabolism of 7-hydroxyflavanone (1) with fungal culture Cunninghamella blakesleeana (ATCC 8688a), yielded flavanone 7-sulfate (2), 7,4'-dihydroxyflavanone (3), 6,7-dihydroxyflavanone (4), 6-hydroxyflavanone 7-sulfate (5), and 7-hydroxyflavanone 6-sulfate (6). Mortierella zonata (ATCC 13309) also transformed 1 to metabolites 2 and 3 as well as 4'-hydroxyflavanone 7-sulfate (7), flavan-4-cis-ol 7-sulfate (8), 2',4'-dihydroxychalcone (9), 7,8-dihydroxyflavanone (10), 8-hydroxyflavanone 7-sulfate (11), and 8-methoxy-7-hydroxyflavanone (12). Beauveria bassiana (ATCC 7159) metabolized 1 to 2, 3, and 8, flavanone 7-O-β-D-O-4-methoxyglucopyranoside (13), and 8-hydroxyflavanone 7-O-β-D-O-4-methoxyglucopyranoside (14). Chaetomium cochlioides (ATCC 10195) also transformed 1 to 2, 3, 9, together with 7-hydroxy-4-cis-ol (15). Mucor ramannianus (ATCC 9628) metabolized 1 in addition to 7, to also 4,2',4'-trihydroxychalcone (16), 7,3',4'-trihydroxyflavanone (17), 4'-hydroxyflavanone 7-O-α-L-rhamnopyranoside (18), and 7,3',4'-trihydroxy-6-methoxyflavanone (19). The organism Aspergillus alliaceus (ATCC 10060) transformed 1 to metabolites 3, 16, 7,8,4'-trihydroxyflavanone (20), and 7-hydroxyflavanone 4'-sulfate (21). A metabolite of 1, flavanone 7-O-β-D-O-glucopyranoside (22) was produced by Rhizopus oryzae (ATCC 11145). Structures of the metabolic products were elucidated by means of spectroscopic data. None of the metabolites tested showed antibacterial, antifungal and antimalarial activities against selected organisms. Metabolites 4 and 16 showed weak antileishmanial activity.     

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.     

Synthese und Chiralität der stereoisomeren Achillene,Achillenole und Hymentherene

(+)-cis-Achillene ( 10 ) and (?)-trans-achillenol (7), two monoterpenes recently isolated [1] from the essential oil of Achilleafilipendulina, were synthesized, together with their stereoisomers (?)-(9) and (+)-(8), starting from (S)-(+)-2,6-trans-dimethylocta-1,3, 7-triene ( 1 ). The isomeric ß-hymen thereties ((?)- 3 and (+)-4), often quoted [2] [3] [4] but never isolated, were obtained as intermediates. The mode of synthesis chosen establishesis (R)-chirality for naturally occurring (?)-trans-achillenol (7) and (+)-cis-achillene ( 10 ) as well as for the purely synthetic 4, 7-diene derivatives described in this paper.     

Benzazole-N(SINGLE BOND)BH3 adducts. Reductive transposition of 2-benzimidazole, 2-benzothiazole,and 2-benzoxazole N(SINGLE BOND)BH3 adducts to 1,3,2-benzimidazaborole, 1,3,2-benzoxaborole,and 1,3,2-benzothiazaborole

1,3,2-Benzimidazaborole, 1,3,2-benzoxaborole, and 1,3,2-benzothiazaborole were synthesized from the corresponding 2-benzazole N(SINGLE BOND)BH₃ and 2-benzazole S(SINGLE BOND)BH₃ adducts through a reductive transposition from the isolobal fragment X(SINGLE BOND)C(sp²) (DOUBLE BOND) N(sp²) (SINGLE BOND) B(sp³) (X (DOUBLE BOND) N, O, S) to the fragment X(SINGLE BOND)B(sp²) (DOUBLE BOND) N(sp²) (SINGLE BOND) C(sp³). N(SINGLE BOND)BH₃ substitution shifts to lower frequencies 4-H, C-3a, and C-7a resonances. The X-ray diffraction analysis of 2-(o-methoxyphenyl)benzothiazole N(SINGLE BOND)BH₃ adduct is reported. Two new tetracyclic boron-bridged compounds were observed as by-products (6,9-(ethyl)-diaza-2-oxa-1-bora[3,4,7,8]-dibenzobycyclo[4.3.0]-nona-3,7-diene, 6d, and 8-aza-9-oxa-2-thia-1-bora-[3,4,7,8]dibenzobycyclo[3.4.0]nona-3,7-diene, 15d, when 2-(o-methoxyphenyl)-1-ethylbenzimidazole-BH₃ 6b and 2-(o-methoxyphenyl)-benzothiazole-BH₃ 15b adducts were heated. © 1996 John Wiley & Sons, Inc.     

Inhibitory effects of constituents from Euphorbia lunulata on differentiation of 3T3-L1 cells and nitric oxide production in RAW264.7 cells

A new flavonol galactopyranoside, myricetin 3-O-(2',3'-digalloyl)-β-D-galactopyranoide (1), and 23 known constituents, including myricetin 3-O-(2'-galloyl)-β-D-galactopyranoide (2), myricitrin (3), myricetin (4), quercetin 3-O-(2', 3'-digalloyl)-β-D-galactopyranoide (5), quercetin 3-O-(2'-galloyl)-β-D-galactopyranoide (6), hyperin (7), isoquercetrin (8), quercetin (9), kaempferol (10), apigenin (11), luteolin (12), 3-O-methylquercetin (13), 5,7,2',5'-tetrahydroxyflavone (14), 1,3,4,6-tetra-O-galloyl-β-D-glucose (15), 1,2,6-tri-O-galloyl-β-D-glucose (16), 1,3,6-tri-O-galloyl-β-D-glucose (17), gallic acid (18), protocatechuic acid (19), 3,4,5-trimethoxybenzoic acid (20), 2,6-dihydroxyacetophenone (21), 3,3'-di-O-methylellagic acid (22), ellagic acid (23) and esculetin (24) were isolated from Euphorbia lunulata Bge. Their structures were determined by spectroscopic analysis. Isolated hydrolysable tannins, flavonoids, and flavonol galactopyranoside gallates showed significant inhibition of the differentiation of 3T3-L1 preadipocytes and triglyceride accumulation in maturing adipocytes, and nitric oxide production in RAW 264.7 cells.