- Asymmetric total synthesis of four bioactive lignans using donor-acceptor cyclopropanes and bioassay of (?)- and (+)-niranthin against hepatitis B and influenza viruses
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The asymmetric total synthesis of four lignans, dimethylmatairesinol, matairesinol, (?)-niranthin, and (+)-niranthin has been achieved using reductive ring-opening of cyclopropanes. Moreover, we performed bioassays of the synthesized (+)- and (?)-niranthins using hepatitis B and influenza viruses, which revealed the relationship between the enantiomeric structure and the anti-viral activity of niranthin.
- Karasawa, Daichi,Nishii, Yoshinori,Oshima, Mizuki,Ota, Ryotaro,Shimasaki, Noriko,Watashi, Koichi
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p. 4635 - 4639
(2022/02/19)
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- Convenient preparation and spectroscopic characterization of 7r-hydroxymatairesinol
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The preparation of 7R-HMR (allo-hydroxymatairesinol) is reported by: (a) NaBH4 kinetic reduction of 7R/7S diastereomeric mixture; and (b) epimerization of the C7 hydroxyl group by Mitsunobu reaction and subsequent ester hydrolysis. The availability of highly pure target compound (7R-HMR) made it possible to confirm the structure of the target compound and to complete the full spectroscopic characterization.
- Ciriello, Umberto,Colombo, Eleonora,Paladino, Giuseppe,Passarella, Daniele
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- Cytotoxic activity of dietary lignan and its derivatives: Structure-cytotoxic activity relationship of dihydroguaiaretic acid
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Cytotoxic activities of synthesized lignan derivatives were estimated by WST-8 reduction assay against HL-60 and HeLa cells to show the structure-activity relationship. The activities of some effective compounds were examined against Colon 26 and Vero cel
- Wukirsari, Tuti,Nishiwaki, Hisashi,Nishi, Kosuke,Sugahara, Takuya,Akiyama, Koichi,Kishida, Taro,Yamauchi, Satoshi
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p. 5305 - 5315
(2014/06/24)
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- Cytotoxic activity of dietary lignan and its derivatives: Structure-cytotoxic activity relationship of dihydroguaiaretic acid
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Cytotoxic activities of synthesized lignan derivatives were estimated by WST-8 reduction assay against HL-60 and HeLa cells to show the structure-activity relationship. The activities of some effective compounds were examined against Colon 26 and Vero cel
- Wukirsari, Tuti,Nishiwaki, Hisashi,Nishi, Kosuke,Sugahara, Takuya,Akiyama, Koichi,Kishida, Taro,Yamauchi, Satoshi
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p. 5305 - 5315
(2015/04/22)
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- Synthesis of sterically hindered chiral 1,4-diols from different lignan-based backbones
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Methods for synthetic modifications of the natural dibenzylbutyrolactone lignan hydroxymatairesinol into chiral 1,4-diols with different lignan-derived backbones have been developed. A stepwise procedure, involving alkylation and oxidation, was shown to b
- Brusentsev, Yury,H?nninen, Mikko M.,Eklund, Patrik
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p. 2423 - 2426
(2013/11/06)
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- An access to chiral β-benzyl-γ-butyrolactones and its application to the synthesis of enantiopure (+)-secoisolariciresinol, (-)-secoisolariciresinol, and (-)-enterolactone
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Both enantiomers of secoisolariciresinol and enantiopure (-)-enterolactone were synthesized through a highly stereoselective convergent synthesis. An Evans diastereoselective alkylation followed by a substrate-induced diastereoselective -alkylation of the newly formed optically active β-benzyl-γ- butyrolactone gave the β-β′ linkage of the target skeleton. The (S,S)- and (R,R)-enantiomers of secoisolariciresinol and (-)-enterolactone were obtained in 12-14% (11 steps) and 20% (7 steps) overall yield, respectively. Georg Thieme Verlag Stuttgart New York.
- Allais, Florent,Pla, Thomas J. L.,Ducrot, Paul-Henri
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experimental part
p. 1456 - 1464
(2011/06/17)
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- Oxidative dehydrogenation of a biomass derived lignan - Hydroxymatairesinol over heterogeneous gold catalysts
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Synthesis of the lignan oxomatairesinol via oxidative dehydrogenation of the naturally occurring lignan hydroxymatairesinol was studied over gold catalysts supported on C, TiO2, SiO2, Al2O 3, and MgO. In order to investigate the reaction performance over the gold catalyst, synthesis of lignan oxomatairesinol was carried out in different organic solvents/water mixtures under synthetic air and nitrogen atmosphere at 373 K, and using also isolated hydroxymatairesinol isomers as a starting material. The results were compared with those obtained over palladium catalysts. Synthesized supported gold catalysts as well as the corresponding supports were characterized by TEM, XRD, ICP-OES, CO2-TPD, FTIR (using pyridine as a probe molecule), and XPS. Gold catalysts were shown to display superior performance compared with palladium ones: the activity was 4 times higher, with selectivity toward oxomatairesinol being 100%, while 60-85% were obtained over palladium catalysts. In contrast to palladium, the activity of gold catalysts is high in aerobic conditions and water-propan-2-ol mixture. However, activity and selectivity of gold catalysts were shown to be dependent on the electronic state of the metal and, similar to palladium catalysts, on the support acidity.
- Simakova, Olga A.,Murzina, Elena V.,Maeki-Arvela, Paeivi,Leino, Anne-Riikka,Campo, Betiana C.,Kordas, Krisztian,Willfoer, Stefan M.,Salmi, Tapio,Murzin, Dmitry Yu.
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experimental part
p. 54 - 64
(2011/09/20)
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- A novel approach towards dibenzylbutyrolactone lignans involving heck and radical reactions: Application to (±)-matairesinol synthesis
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A highly regio- and stereoselective Heck reaction of iodoarenes with vinylated malonates, generated in situ by fluoride-induced protiodesilylation of alkenylsilanols/disiloxanes to give functionalized styrenes and 1,4-diaryl-1-butenes has been developed. The dibenzylbutyrolactone lignan skeletons have been achieved from 1,4-diaryl-1-butenes by two routes involving diastereoselective radical cyclization as the key step. This strategy has successfully been applied in the synthesis of (±)-matairesinol. Wiley-VCH Verlag GmbH & Co. KGaA, 2007.
- Singh, Rekha,Singh, Gobind C.,Ghosh, Sunil K.
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p. 5376 - 5385
(2008/03/14)
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- Regioselective oxidative coupling approach to the synthesis of (±)-matairesinol and (±)-secoisolariciresinol
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An efficient method for the synthesis of (±)-matairesinol and (±)-secoisolariciresinol is presented. By using 5-(tert-butyl)ferulic acid as a precursor, a regioselective oxidative coupling step was realized, which gave the desired coupling product in much higher yield (91%) than the literature value (ca. 20%). Georg Thieme Verlag Stuttgart.
- Zhu, Fuqiang,Li, Wenling,Wang, Qian,Hou, Zijie
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p. 1780 - 1782
(2008/02/04)
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- Secoisolariciresinol dehydrogenase: Mode of catalysis and stereospecificity of hydride transfer in Podophyllum peltatum
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Secoisolariciresinol dehydrogenase (SDH) catalyzes the NAD+ dependent enantiospecific conversion of secoisolariciresinol into matairesinol. In Podophyllum species, (-)-matairesinol is metabolized into the antiviral compound, podophyllotoxin, wh
- Moinuddin, Syed G.A.,Youn, Buhyun,Bedgar, Diana L.,Costa, Michael A.,Helms, Gregory L.,Kang, Chulhee,Davin, Laurence B.,Lewis, Norman G.
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p. 808 - 816
(2007/10/03)
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- Reactions of hydroxymatairesinol over supported palladium catalysts
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In this work, hydroxymatairesinol (extracted from Norway spruce knots) was hydrogenolyzed to matairesinol over palladium impregnated H-Beta-300, H-Beta-150, H-Beta-25, H-Beta-11, H-Y, H-Mordenite, H-MCM-41, H-ZSM-5, SiO 2, and Al2O3. H-Beta-25 without palladium was also investigated. The hydrogenolysis was performed in 2-propanol at 70 °C under hydrogen and nitrogen atmospheres in a stirred glass reactor. The catalysts were characterized by nitrogen physisorption, direct current plasma atomic emission spectrometry, X-ray powder diffraction, CO pulse chemisorption, transmission electron microscopy, and Fourier transform infrared spectroscopy (pyridine adsorption). Palladium on H-Beta with different acidities was tested; the results showed that the reaction rate was inversely proportional to the acidity. However, Bronsted acid sites are needed for the reaction, because palladium on SiO2 and Al2O3 is not active. In addition to the acidity, a metal is needed; the H-Beta-25 support without palladium displays no activity.
- Markus, Heidi,Maeki-Arvela, Paeivi,Kumar, Narendra,Heikkilae, Teemu,Lehto, Vesa-Pekka,Sjoeholm, Rainer,Holmbom, Bjarne,Salmi, Tapio,Murzin, Dmitry Yu.
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p. 301 - 308
(2007/10/03)
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- Effect of benzylic oxygen on the antioxidant activity of phenolic lignans
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It has been clarified in the present investigation that a high degree of oxidation at the benzylic position of phenolic lignans bearing a 4-hydroxy-3-methoxybenzyl group reduces their antioxidant activity and that the antioxidant activity of the bis(4-hydroxy-3-methoxybenzyl)tetrahydrofuran lignan 2 is higher than that of the corresponding y-butyrolactone lignan 1. This was demonstrated by comparing the antioxidant activities of compounds 1 and 2 with those of the (benzyl)(hydroxybenzyl)tetrahydrofurans 3 and 4, the bis(hydroxybenzyl)tetrahydrofurans 7 and 8, the (benzoyl)(benzyl)tetrahydrofuran 6, and the dibenzoyltetrahydrofuran 9. The activity level of compound 2 was approximately the same potency as that of the tetrahydronaphthalene- tetrahydrofuran 5. These compounds possess either a 4-hydroxy-3-methoxybenzyl group or a 4-hydroxy-3-methoxybenzoyl group as the benzyl or benzoyl group. An examination of radical scavenging activity showed differences of activity between diastereomers. To make this comparison possible, compounds 1-9 were synthesized using new synthetic routes for several of these lignans. In this investigation, stereoisomers of the (benzyl)(hydroxybenzyl)tetrahydrofurans 3 and 4 and liovils 7 and 8 were synthesized for the first time.
- Yamauchi, Satoshi,Hayashi, Yoshimasa,Nakashima, Yuki,Kirikihira, Takuya,Yamada, Kazuki,Masuda, Toshiya
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p. 1459 - 1470
(2008/09/18)
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- SYNTHESIS OF 13C-LABELLED ESTROGEN ANALOGUES
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There is provided a method of producing novel 13C-labelled estrogen analogues. The method preferably proceeds via an intermediate A or B or which is a mixture of (A) or (B): wherein a13C atom is located at one or more of positions 1, 2, 3 or 4 and wherein R is an optionally substituted alkane, alkene, alkyne or aryl group. Preferably R is -CH2Ph. An alternative preferred intermediate compound is 13C-resorcinol.
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- Radical carboxyarylation approach to lignans. Total synthesis of (-)-arctigenin, (-)-matairesinol, and related natural products
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Total syntheses of seven biologically important lignan natural products, including (-)-arctigenin, (-)-matairesinol, and (-)α-conidendrin, by way of a highly stereoselective domino radical sequence is presented. The reported stereochemistry of the natural product 7-hydroxyarctigenin is shown to be erroneous; a diastereoisomeric structure is assigned to the natural product.
- Fischer, Joshua,Reynolds, Aaron J.,Sharp, Lisa A.,Sherburn, Michael S.
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p. 1345 - 1348
(2007/10/03)
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- Synthesis of (-)-matairesinol, (-)-enterolactone, and (-)-enterodiol from the natural lignan hydroxymatairesinol.
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[reaction: see text] We describe here a four-step semisynthetic method for the preparation of enantiomerically pure (-)-enterolactone starting from the readily available lignan hydroxymatairesinol from Norway spruce (Picea abies). Hydroxymatairesinol was
- Eklund, Patrik,Lindholm, Anna,Mikkola, J-P,Smeds, Annika,Lehtilae, Reko,Sjoeholm, Rainer
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p. 491 - 493
(2007/10/03)
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- Dirigent-mediated podophyllotoxin biosynthesis in Linum flavum and Podophyllum peltatum
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Given the importance of the antitumor/antiviral lignans, podophyllotoxin and 5-methoxypodophyllotoxin, as biotechnological targets, their biosynthetic pathways were investigated in Podophyllum peltatum and Linum flavum. Entry into their pathways was established to occur via dirigent mediated coupling of E-coniferyl alcohol to afford (+)-pinoresinol; the encoding gene was cloned and the recombinant protein subsequently obtained. Radiolabeled substrate studies using partially purified enzyme preparations next revealed (+)-pinoresinol was enantiospecifically converted sequentially into (+)-lariciresinol and (-)-secoisolariciresinol via the action of an NADPH-dependent bifunctional pinoresinol/lariciresinol reductase. The resulting (-)-secoisolariciresinol was enantiospecifically dehydrogenated into (-)-matairesinol, as evidenced through the conversion of both radio- and stable isotopically labeled secoisolariciresinol into matairesinol, this being catalyzed by the NAD-dependent secoisolariciresinol dehydrogenase. (-)-Matairesinol was further hydroxylated to afford 7'-hydroxymatairesinol, this being efficiently metabolized into 5-methoxypodophyllotoxin. Thus much of the overall biosynthetic pathway to podophyllotoxin has been established, that is, from the dirigent mediated coupling of E-coniferyl alcohol to the subsequent conversions leading to 7'-hydroxymatairesinol. (C) 2000 Elsevier Science Ltd.
- Xia, Zhi-Qiang,Costa, Michael A,Proctor, John,Davin, Laurence B,Lewis, Norman G
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p. 537 - 549
(2007/10/03)
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- New synthetic route to butanolide lignans by a ruthenium complex catalyzed hydrogenation of the corresponding Stobbe's fulgenic acids
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A new two-step total synthesis of butanolide lignans (or dibenzylbutyrolactone lignans) is described, which affords the title compounds in good yield and with a very short work-up time. It involves a ruthenium carbonyl hydride complex-catalyzed hydrogenation of the corresponding dibenzylidene succinic acids (fulgenic acids). Since the catalytic hydrogenation (second step) is a total yielding process, the overall yield determining step is the preparation of the fulgenic acid intermediates by the Stobbe condensation (first step), which has consequently been revised to improve many details. This simple process moreover allows hexadeuterated butanolide lignans to be readily obtained for isotopic dilution mass spectral measurements. The syntheses of a selection of lignans, namely enterolactone, matairesinol, hinokinin, dimethylmatairesinol and cordigerine, are described to illustrate the whole procedure.
- Bambagiotti-Alberti, Massimo,Coran, Silvia A.,Vincieri, Franco F.,Mulinacci, Nadia,Pieraccini, Giuseppe M.L.
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p. 2185 - 2196
(2007/10/02)
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- THE SYNTHESES OF (R)-(+)-β-VANILLYL-γ-BUTYROLACTONE AND OF CHIRAL LIGNANS THEREFROM
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(R)-(+)-β-vanillyl-γ-butyrolactone was obtained in 4 steps including a resolution, from vanillin and dimethyl succinate, and was used for the total syntheses of 5 naturally occurring and optically active lignans such as (+)-isolariciresinol 20.
- Brown, Eric,Daugan, Alain
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p. 1169 - 1172
(2007/10/02)
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- Lignans from Trachelospermum asiaticum (Tracheolospermum . II)
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Lignans of Trachelospermum asiaticum were isolated from the polar fraction of the methanol percolate, and the structures were determined.Trachelosiaside (matairesinol 5'-C-β-D-glucoside) was isolated as the first naturally occurring C-glucoside of lignan.
- Abe, Fumiko,Yamauchi, Tatsuo
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p. 4340 - 4345
(2007/10/02)
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