- Using α- and β-Epimerizations of cis-2,3-Bis(hydroxymethyl)-γ-butyrolactone for the Synthesis of Both Enantiomers of Enterolactone
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In the context of asymmetric synthesis, epimerization is usually problematic. Here, we describe the use of the epimerization of cis-2,3-bis(hydroxymethyl)-γ-butyrolactone for the synthesis of enterolactones with anti-carcinogenic, anti-inflammatory, anti-angiogenic, and antioxidant activity. Selective α- or β-epimerization of a γ-butyrolactone was used to selectively synthesize both enantiomers of enterolactone. Theoretical and kinetic studies were performed to elucidate the epimerization mechanism.
- Jiang, Rui,Ismiyarto,Abe, Tsukasa,Zhou, Da-Yang,Asano, Kaori,Suzuki, Takayoshi,Sasai, Hiroaki,Suzuki, Takeyuki
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p. 5051 - 5056
(2022/03/16)
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- Enantiomerically Enriched α-Borylzinc Reagents by Nickel-Catalyzed Carbozincation of Vinylboronic Esters
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In this paper is described a synthesis of enantiomerically enriched, configurationally stable organozinc reagents by catalytic enantioselective carbozincation of a vinylboronic ester. This process furnishes enantiomerically enriched α-borylzinc intermediates that are shown to undergo stereospecific reactions, producing enantioenriched secondary boronic ester products. The properties of the intermediate α-borylzinc reagent are probed and the synthetic utility of the products is demonstrated by application to the synthesis of (-)-aphanorphine and (-)-enterolactone.
- Chen, Jingjia,Hu, Weipeng,Jin, Jing,Lovinger, Gabriel J.,Morken, James P.,Zhang, Chenlong
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supporting information
p. 14189 - 14195
(2021/09/11)
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- Isolation and characterization of a human intestinal bacterium Eggerthella sp. CAT-1 capable of cleaving the C-Ring of (+)-catechin and (-)-Epicatechin, followed by p-dehydroxylation of the B-ring
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We isolated a human intestinal bacterium, capable of cleaving the C-ring and dehydroxylating the Bring of both (+)-catechin (2 R ,3S ) and (-)-epicatechin (2 R ,3R). Although the strain was classified as Eggerthella (Eg.) lenta [named Eg. sp. CAT-1 (JF798636)] by 16S ribosomal RNA (rRNA) gene similarity, it was quite different in substrate specificity from a previously isolated strain, Eg. sp. SDG-2, which takes part in cleavage of the C-ring and dehydroxylation of the 3,4-dihydroxyphenyl moiety (B-ring) of (3R)-flavan-3-ol derivatives. On the other hand, both Eg. sp. CAT-1 and Eg. sp. SDG-2 showed the same substrate specificity against dehydroxylation of enantiomeric lignans, (+)- and (-)-dihydroxyenterodiol, and (+)- and (-)-dihydroxyenterolactone.
- Jin, Jong-Sik,Hattori, Masao
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p. 2252 - 2256
(2013/02/23)
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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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- Asymmetric syntheses of (-)-enterolactone and 7′R)-7′- hydroxyenterolactone via organocatalyzed aldol reaction
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(Chemical Equation Presented) Short syntheses of (-)-enterolactone (1a) and (7′R)-7′-hydroxyenterolactone (1b) have been achieved utilizing organocatalyzed asymmetric cross-aldol reaction of aldehydes 2 and 3 and base-mediated alkylation of lactones 5 and 4.
- Hajra, Saumen,Giri, Aswini Kumar,Hazra, Sunit
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supporting information; experimental part
p. 7978 - 7981
(2010/02/28)
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- Further studies on a human intestinal bacterium Ruminococcus sp. END-1 for transformation of plant lignans to mammalian lignans
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A human intestinal bacterium Ruminococcus (R.) sp. END-1 capable of oxidizing (-)-enterodiol to (-)-enterolactone, enantioselectively, was further investigated from the perspective of transformation of plant lignans to mammalian lignans; A cell-free extra
- Jin, Jong-Sik,Hattori, Masao
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experimental part
p. 7537 - 7542
(2010/07/08)
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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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- 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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- Transformation of arctiin to estrogenic and antiestrogenic substances by human intestinal bacteria
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After anaerobic incubation of arctiin (1) from the seeds of Arctium lappa with a human fecal suspension, six metabolites were formed, and their structures were identified as (-)-arctigenin (2), (2R,3R)-2-(3′,4′- dihydroxybenzyl)-3-(3″,4″-dimethoxybenzyl)b
- Xie, Li-Hua,Ahn, Eun-Mi,Akao, Teruaki,Abdel-Hafez, Atef Abdel-Monem,Nakamura, Norio,Hattori, Masao
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p. 378 - 384
(2007/10/03)
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- A short synthesis of both enantiomers of enterolactone
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A short and efficient synthesis of both enantiomers of enterolactone, a mammalian lignan, is described. The overall yield for the natural enterolactone, over seven steps, was 19% and for its enantiomer 27%.
- Sibi, Mukund P.,Liu, Pingrong,Johnson, Michael D.
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p. 133 - 138
(2007/10/03)
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- Chemoenzymatic enantioselective synthesis of (-)-enterolactone
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Enterolactone, a lignan isolated from biological fluids of animals and humans, was synthesized via enzymatic desymmetrization of 2-(3-methoxybenzyl)-1,3-propanediol.
- Chenevert, Robert,Mohammadi-Ziarani, Ghodsi,Caron, Dave,Dasser, Mohammed
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p. 223 - 226
(2007/10/03)
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- Oxidative metabolism of the mammalian lignans enterolactone and enterodiol by rat, pig, and human liver microsomes
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Hepatic microsomes from aroclor-treated male Wistar rats biotransform enterolactone to 12 metabolites, six of which carry an additional hydroxy group at the aromatic and six at the aliphatic moiety according to HPLC/MS and GC/MS analysis. The aromatic hyd
- Jacobs, Eric,Metzler, Manfred
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p. 1071 - 1077
(2007/10/03)
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- Intramolecular regioselective insertion into unactivated prochiral carbon-hydrogen bonds with diazoacetates of primary alcohols catalyzed by chiral dirhodium(II) carboxamidates. Highly enantioselective total synthesis of natural lignan lactones
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Intramolecular insertion into unactivated prochiral C-H bonds of 3-aryl-1-propyl diazoacetates catalyzed by dirhodium(II) tetrakis[methyl 1-(3-phenyl propanoyl)imidazolidin-2-one-4(R or S)-carboxylate], Rh2(4R-MPPIM)4 or Rh2(4S-MPPIM)4, occurs in 91-96% ee and with virtually complete regiocontrol for the formation of β-benzyl-γ-butyrolactones. This methodology has been applied to the total synthesis of dibenzylbutyrolactone lignans (-)- and (+)-enterolactone, (-)- and (+)-hinokinin, and (+)-arctigenin from substituted cinnamic acids in 19-27% overall yields. Aryltetralin lignan (+)-isodeoxypodophyllotoxin was prepared from the reactant 3,4-(methylenedioxy)cinnamic acid in 36% yield overall, and the lactone precursor to (+)-isolauricerisinol was formed in 96.5% ee and 23% yield overall. Applications of the chiral Rh2(MPPIM)4 catalysts to fully aliphatic systems resulting in the formation of β-substituted-γ-butyrolactones with high regiocontrol and with 93-96% ee have demonstrated the generality of this methodology. A model that provides accurate predictions of β-substituted-γ-butyrolactone absolute configurations in these asymmetric metal carbene transformations is described.
- Bode,Doyle,Protopopova,Zhou
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p. 9146 - 9155
(2007/10/03)
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- Enantioselective synthesis of natural dibenzylbutyrolactone lignans (-)-enterolactone, (-)-hinokinin, (-)-pluviatolide, (-)-enterodiol, and furofuran lignan (-)-eudesmin via tandem conjugate addition to γ-alkoxybutenolides1,2
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A general and efficient method is described for the asymmetric synthesis of a variety of liguans. 5-(Menthyloxy)-2(5H)-furanones 5 proved to be excellent chiral synthons in this respect and could be transformed with complete stereoselectivity into a number of lignans. The addition of lithiated dithianes 7 to enantiomerically pure butenolides 5 was followed by quenching of the resulting lactone enolate anions with a benzylbromide (9) or with an aldehyde (6). This tandem addition quenching procedure gave the diastereomerically pure adducts 11, 26, or 27 in 50-67% yield, with a carbon skeleton as found in most natural lignans. As examples of the wide applicability of this method, the syntheses of the enantiomerically pure natural lignans (-)-hinokinin (23b), (-)-enterolactone (24a), (-)-pluviatolide (24c), and (-)-enterodiol (25) in overall yields of 29-37% from 5a and (-)eudesmin (30) in 16% overall yield from 5b are described.
- Van Oeveren,Jansen,Feringa
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p. 5999 - 6007
(2007/10/02)
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- Novel stereoselective synthesis of (-)-enterolactone employing chiral unsaturated lactam
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A novel convergent synthetic methodology of chiral antileukemic lignan lactones was developed by the use of optically active N-alkyl-α,β-unsaturated lactam elaborated from L-malic acid and the asymmetric synthesis of (-)-enterolactone was accomplished in short and simple steps.
- Yoda, Hidemi,Kitayama, Hidekazu,Katagiri, Takao,Takabe, Kunihiko
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p. 3313 - 3322
(2007/10/02)
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- 3-Substituted-γ-butyrolactones from 5-Trimethylsilyl-2-cyclohexenone. Synthesis of (-)-Enterolactone
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1,4-Adducts of 5-trimethylsilyl-2-cyclohexenone (1) with Grignard reagents were converted to various hexanoate derivatives and γ-butyrolactones.Starting from optically pure 1, (-)-enterolactone (Factor X) was synthesized.
- Asaoka, Morio,Fujii, Naoaki,Shima, Kunihisa,Takei, Hisashi
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p. 805 - 808
(2007/10/02)
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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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- CONVENIENT RUTHENIUM-COMPLEX CATALYSED SYNTHESIS OF ENTEROLACTONE FROM THE CORRESPONDING DIBENZYLIDENE SUCCINIC ACID MOIETY
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A convenient synthesis of enterolactone is outlined consisting mainly of a ruthenium carbonyl-hydride complex catalysed hydrogenation of bis(3-methoxybenzylidene)succinic acid.
- Bambagiotti-Alberti, Massimo,Coran, Silvia A.,Vincieri, Franco F.,Nostro, Pierandrea Lo
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p. 1735 - 1738
(2007/10/02)
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- OXIDATIVE COUPLING. II. THE TOTAL SYNTHESIS OF ENTEROLACTONE
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Oxidative coupling of 3-methoxyhydrocinnamic acid dianion with molecular iodine forms the key step in an efficient synthesis of enterolactone.
- Belletire, J. L.,Fremont, S. L.
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p. 127 - 130
(2007/10/02)
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- Synthesis of the 2H>-Labelled Urinary Lignans Enterolactone and Enterodiol
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Isotopically labelled forms of urinary lignans (+/-)-trans-2,3-bis-(3-hydroxybenzyl)butan-4-olide (enterolactone) and (+/-)2,3-bis-(3-hydroxybenzyl)butane-1,4-diol (enterodiol) have been synthesized from 2H2>butenolide, obtained from the furan-maleic anhydride adduct by reduction (NaBD4) and pyrolysis.
- Kirk, N. David,McLaughlin, Leo M.,Lawson, Alexander M.,Setchell, Kenneth D.R.,Patel, Shailesh K.
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- Synthesis of Lignan Lactones by Conjugate Addition of Thioacetal Carbanions to Butenolide
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The conjugate addition of carbanions derived from arylbis(phenylthio)methanes to butenolide followed by trapping of the enolate anion so generated by a benzyl halide affords adducts (8) containing the basic lignan skeleton.Desulphurisation of these adducts by Raney nickel affords a short efficient synthesis of trans-dibenzylbutyrolactones and this route has been used to prepare enterolactone (9c) and an antitumour lignan (9b), derived from Bursera schlechtendalii.Treatment of the adducts (8) with heavy-metal salts induces cyclisation leading to arylnaphthalene lactones, including retrojusticidin B (13).
- Pelter, Andrew,Ward, Robert S.,Satyanarayana, Panchagnula,Collins, Peter
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p. 643 - 647
(2007/10/02)
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- DIMETALATED TERTIARY SUCCINAMIDES. SYNTHESIS OF SEVERAL CLASSES OF LIGNANS INCLUDING THE MAMMALIAN URINARY LIGNANS ENTEROLACTONE AND ENTERODIOL
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Reaction of dimetalated succinamides with benzyl halides and aromatic aldehydes provides short routes to diverse lignan natural products 2, 3, and 4a, including the human urinary metabolites (3d) and (2e).
- Mahalanabis, K.K.,Mumtaz, M.,Snieckus, V.
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p. 3975 - 3978
(2007/10/02)
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- CHEMICAL SYNTHESIS OF THE FIRST LIGNANS TO BE FOUND IN HUMANS AND ANIMALS
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Trans-2,3-bis-(3'-hydroxybenzyl)-butyrolactone (1) and 2,3-bis-(3'-hydroxybenzyl)-butane-1,4-diol (2), recently identified in urine, have been synthesised in racemic form.
- Cooley, George,Farrant, R. Duncan,Kirk, David N.,Wynn, Steven
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p. 349 - 350
(2007/10/02)
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- SYNTHESIS OF COMPOUND X, A NON-STEROIDAL CONSTITUENT OF FEMALE URINE, AND CONGENERS
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The synthesis of trans-(+/-)- and (-)-3,4-bisdihydro-2-(3H)-furanone (1), a recently discovered constituent of female urine, and some related compounds of biological interest is described.
- Groen, M.B.,Leemhuis, J.
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p. 5043 - 5046
(2007/10/02)
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