347359-71-1Relevant academic research and scientific papers
α,β-Dibenzyl-γ-butyrolactone lignan alcohols: total sytnhesis of (+/-)-7'-hydroxyenterolactone, (+/-)-7'-hydroxymatairesinol and (+/-)-8-hydroxyenterolactone
Maekelae, Taru H.,Kaltia, Seppo A.,Waehaelae, Kristiina T.,Hase, Tapio A.
, p. 777 - 784 (2001)
Two trans-α,β-dibenzyl-γ-butyrolactone lignans carrying a hydroxyl group at the β-benzylic carbon aton and a α-hydroxy α,β-dibenzyl-γ-butyrolactone lignan were synthesized in racemic form using the tandem conjugate addition reaction to construct the basic lignan skeleton. Subsequent reaction steps involved either a catalytic reduction of the regenerted keto group to the alcohol, or a hydrogenolysis to benzylic methylene followed by lactone enolate formation and oxidation to give the α-hydroxybutyrolactones. These procedures were applied for the synthesis of 7'-hydroxyenterolactones and 7'-hydroxymatairesinols, and 8-hydroxyenterolacotones, respectively. The diastereomeric mixtures of these compounds were separated either by HPLC techniques or column chromatography and the structures were elucidated using NMR spectroscopy.
Stereoselective synthesis of β-(hydroxymethylaryl/alkyl)-α- methylene-γ-butyrolactones
Hodgson, David M.,Talbot, Eric P. A.,Clark, Barry P.
, p. 2594 - 2597 (2011)
Zinc or a chromium(II) source with 3-(bromomethyl)furan-2(5H)-one (3) and an aldehyde gives β-(hydroxymethylaryl/alkyl)-α-methylene-γ- butyrolactones 5 in good yields and high diastereoselectivities. The methodology is demonstrated in concise syntheses of (±)-hydroxymatairesinol (8) and (±)-methylenolactocin (10) by subsequent arylboronate conjugate addition and translactonization, respectively.
Convenient preparation and spectroscopic characterization of 7r-hydroxymatairesinol
Ciriello, Umberto,Colombo, Eleonora,Paladino, Giuseppe,Passarella, Daniele
, (2021/09/30)
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.
TRIP-Catalyzed Asymmetric Synthesis of (+)-Yatein, (-)-α-Conidendrin, (+)-Isostegane, and (+)-Neoisostegane
Hartmann, Peter,Lazzarotto, Mattia,Steiner, Lorenz,Cigan, Emmanuel,Poschenrieder, Silvan,Sagmeister, Peter,Fuchs, Michael
, p. 5831 - 5837 (2019/04/25)
The asymmetric allylation under the assistance of catalytic amounts of 3,3′-bis(2,4,6-triisopropylphenyl)-1,1′-binaphthyl-2,2′-diyl hydrogen phosphate (TRIP) allows the concise construction of the lignan scaffold from simple aldehydes and allylic bromides with full control of the two formed stereocenters. This young methodology has been employed to synthesize four naturally and pharmaceutically active lignans. Members of the dibenzylbutyrolactone, the tetraline, and the dibenzocyclooctadiene classes have been synthesized in 40-47% overall yield along four-step synthetic routes.
Asymmetric aldol approach to dibenzylbutyrolactone lignans: Synthesis of (-)-(7′S)-hydroxymatairesinol and (-)-(7′S)-hydroxyarctigenin
Hajra, Saumen,Mandal, Abhisek,Hazra, Sunit
supporting information, p. 2171 - 2173 (2013/05/08)
A competent and general asymmetric synthesis of 7′- hydroxydibenzylbutyrolactone lignans such as (7′S)-hydroxymatairesinol and (7′S)-hydroxyarctigenin has been reported from N-succinyl-2-oxazolidinone in six steps where diastereoselective aldol reaction and stereoselective alkylation serve as the key steps.
Asymmetric synthesis of β-substituted α-methylenebutyro-lactones via trip-catalyzed allylation: Mechanistic studies and application to the synthesis of (S)-(-)-hydroxymatairesinol
Fuchs, Michael,Schober, Markus,Orthaber, Andreas,Faber, Kurt
, p. 2499 - 2505 (2013/10/21)
Asymmetric allylation of (hetero)aromatic aldehydes by a zinc(II)-allylbutyrolactone species catalyzed by a chiral BINOL-type phosphoric acid gave β-substituted α-methylenebutyrolactones in 68 to >99% ee and 52-91% isolated yield. DFT studies on the intermediate Zn 2+-complex - crucial for chiral induction - suggest a six-membered ring intermediate, which allows the phosphoric acid moiety to activate the aldehyde. The methodology was applied to the synthesis of the antitumour natural product (S)-(-)-hydroxymatairesinol.
Oxidative dehydrogenation of a biomass derived lignan - Hydroxymatairesinol over heterogeneous gold catalysts
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.
experimental part, p. 54 - 64 (2011/09/20)
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.
Asymmetric synthesis, stereochemistry and rearrangement reactions of naturally occurring 7′-hydroxylignano-9,9′-lactones
Raffaelli, Barbara,Waehaelae, Kristiina,Hase, Tapio
, p. 331 - 341 (2008/01/27)
The asymmetric synthesis of a series of (7′S,8R,8′R)-7′- hydroxylignano-9,9′-lactones is presented, among them the mammalian lignan (7′S)-hydroxyenterolactone and (7′S)-parabenzlactone, allowing the stereochemistry of natural occurring (-)-parabenzlactone
Radical carboxyarylation approach to lignans. Total synthesis of (-)-arctigenin, (-)-matairesinol, and related natural products
Fischer, Joshua,Reynolds, Aaron J.,Sharp, Lisa A.,Sherburn, Michael S.
, p. 1345 - 1348 (2007/10/03)
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.
Dirigent-mediated podophyllotoxin biosynthesis in Linum flavum and Podophyllum peltatum
Xia, Zhi-Qiang,Costa, Michael A,Proctor, John,Davin, Laurence B,Lewis, Norman G
, p. 537 - 549 (2007/10/03)
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.
