- Linderapyrone: A Wnt signal inhibitor isolated from Lindera umbellata
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Linderapyrone, a Wnt signal inhibitor was isolated from the methanolic extract of the stems and twigs of Lindera umbellata together with epi-(-)-linderol A. Linderapyrone inhibited TCF/β-catenin transcriptional activity that was evaluated using cell-based TOPFlash luciferase assay system. To evaluate the structure-activity relationship and mechanism, we synthesized linderapyrone and its derivatives from piperitone. As the results of further bioassay for synthesized compounds, we found both of pyrone and monoterpene moieties were necessary for inhibitory effect. cDNA microarray analysis in a linderapyrone derivative treated human colorectal cancer cells showed that this compound downregulates Wnt signaling pathway. Moreover, we successes to synthesize the derivative of linderapyrone that has stronger inhibitory effect than linderapyrone and ICG-001 (positive control).
- Matsumoto, Takahiro,Kitagawa, Takahiro,Imahori, Daisuke,Matsuzaki, Atsushi,Saito, Youhei,Ohta, Tomoe,Yoshida, Tatsusada,Nakayama, Yuji,Ashihara, Eishi,Watanabe, Tetsushi
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supporting information
(2021/06/07)
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- Transition-Metal-Free Allylic Borylation of 1,3-Dienes
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This work explains the reactivity of diboron reagents with 1,3-dienes in a transition-metal-free context. The sole addition of Na2CO3 (30 mol %) to bis(pinacolato)diboron in MeOH allows the 1,4-hydroboration of cyclic and noncyclic 1,3-dienes. The electronic influence on the substrate guarantees the conjugated 1,4-hydroboration versus 1,2-diboration. DFT calculations show that the distribution of charge in the allylic anion intermediate governs the selectivity toward 1,4-hydroboration, while the favored trans configuration in diene reagents determines the preference for the E allyl boronate products.
- Maza, Ricardo J.,Davenport, Elliot,Miralles, Núria,Carbó, Jorge J.,Fernández, Elena
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supporting information
p. 2251 - 2255
(2019/04/10)
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- Enantioselective Total Syntheses of (+)-Hostmanin A, (-)-Linderol A, (+)-Methyllinderatin and Structural Reassignment of Adunctin E
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A one-step protocol has been developed for the enantioselective synthesis of hexahydrodibenzofuran derivatives using a modified Friedel-Crafts reaction. The developed method was applied to the synthesis of a series of natural products including (+)-hostmanin A, (+)-methyllinderatin, and (-)-linderol A. The synthetic and spectroscopic data investigations led to the structural reassignment of natural product adunctin E, which was further confirmed by single-crystal X-ray analysis. (Chemical Presented).
- Dethe, Dattatraya H.,Dherange, Balu D.
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p. 4526 - 4531
(2015/05/13)
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- Enzymatic resolution of racemic secondary cyclic allylic alcohols
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The resolutions of five racemic cyclic alcohols: 6,6-dimethylcyclohex-2-en-1-ol (±)-5, 4,4-dimethylcyclohex-2-en-1-ol (±)-7, 5,5-dimethylcyclohex-2-en-1-ol (±)-11 and isomeric trans-(±)-13 and cis-piperitols (±)-14 are presented. They were resolved by enzymatic esterification with vinyl esters or by enzymatic hydrolysis of their racemic esters in phosphate buffer. The following lipases were used as biocatalysts: Novozyme 435 (Candida antarctica), Amano PS (Burkholderia cepacia) and lipase from Candida cylindracea. All isomers of alcohols were obtained with at least 96% ee.
- Winska, Katarzyna,Grudniewska, Aleksandra,Chojnacka, Anna,Bialonska, Agata,Wawrzenczyk, Czeslaw
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experimental part
p. 670 - 678
(2010/08/07)
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- Enantiomeric differentiation of oxygenated p-menthane derivatives by 13C NMR using Yb(hfc)3
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The 13C NMR behaviour of 21 p-menthanic terpene bearing an oxygenated function (alcohol, ketone, acetate) was examined in the presence of a chiral lanthanide shift reagent (Yb(hfc)3). For each monocyclic compound, we measured the lanthanide-induced shift (LIS) on the signals of the carbons and the splitting of signals allowing the enantiomeric differentiation. Some general features were found about their LIS behaviour: experimental data establishing distinct patterns for carvomenthone-like compounds and menthone-like compounds. The enantiomeric splitting was observed for the majority of signals in the spectrum of each compound. In the case of alcohols and acetates, the influence of the relative stereochemistry (cis vs trans) of isopropyl(ene) and the binding function was discussed. Copyright
- Lanfranchi, Don Antoine,Blanc, Marie-Cecile,Vellutini, Muriel,Bradesi, Pascale,Casanova, Joseph,Tomi, Felix
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experimental part
p. 1188 - 1194
(2009/05/26)
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- Lipase-catalyzed resolution of p-menthan-3-ols monoterpenes: Preparation of the enantiomer-enriched forms of menthol, isopulegol, trans- and cis-piperitol, and cis-isopiperitenol
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A study on the enzymic resolution of the most common p-menthan-3-ol monoterpene isomers is described. Enantioenriched alcohols 1, 5, 10, 11 and 12 are obtained by means of the lipase-mediated kinetic acetylation of the corresponding racemic materials. The stereochemical aspects of the enzymic process have been investigated. We found that the structural features of the starting p-menthan-3-ol as well as the kind of lipase used, impacted strongly on the enantioselectivity of the resolution. The potentialities of this approach for preparative purposes are discussed.
- Serra, Stefano,Brenna, Elisabetta,Fuganti, Claudio,Maggioni, Francesco
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p. 3313 - 3319
(2007/10/03)
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- Microbial Allyl Rearrangement and Resolution of Acetates of Unsaturated Cyclic Terpene Alcohols by Pseudomonas sp. NOF-5 Strain
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Microbial hydrolysis of the acetates of unsaturated cyclic terpene alcohols by Pseudomonas sp.NOF-5 isolated from soil was investigated. (+/-)-trans-Carveyl acetate ((+/-)-trans-3) was enantioselectively hydrolyzed with NOF-5 strain to give (-)-trans-carveol ((-)-trans-2 of 86.6percent optical purity).However, the hydrolysis of (+/-)-cis-3 was less enantioselective, while (+/-)-piperitylacetate ((+/-)-6, a cis and trans mixture) was hydrolyzed to give the (-)-trans- and (-)-cis-piperitols ((-)-trans-5 and (-)-cis-5) in a poor optical yield.In this case, other tert-alcohols, (+)-trans- and (-)-cis-2-p-menthen-1-ols ((+/-)-trans-7 and (-)-cis-7, were also produced.Furthermore, microbial and enzymic allyl rearrangements of (+)-trans-6 and (-)-trans-verbenylacetate ((-)-trans-11) were studied.Biological treatment of (+)-trans-6 and (-)-trans-11 with NOF-5 or its esterase gave (+)-trans- and (-)-cis-7 and (+)-cis-3-pinen-2-ol ((+)-cis-12), respectively.
- Inagaki, Takashi,Ueda, Hiroo
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p. 2635 - 2640
(2007/10/02)
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- Carvone- and Piperitone-Derived Allylic Stannanes and Aspects of Their Electrophilic Substitution
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cis- and trans-Carvotanacetols and -piperitols have been converted into the corresponding allylic chlorides, which were made to react with both trimethyltinlithium and triphenyltinlithium.The resulting allylic stannanes were characterized by 1H, 13C and 119Sn n.m.r. spectroscopy, which permitted assignment of the relative configurations.Triphenyltinlithium appears to react in a (substantially) concerted fashion with the (optically active) chloride from the carvotanacetols yielding an optically active stannane.The corresponding trimethylstannane is optically inactive.Substitution reactions (SE') with acid and sulfur dioxide (in chloroform) are preferentially γ-anti and specifically γ-syn respectively, in line with conclusions based on other cyclohex-2-enyl systems.
- Young, David,Jones, Martin,Kitching, William
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p. 563 - 573
(2007/10/02)
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- COMPOSITION OF ESSENTIAL OIL FROM LEAVES OF EUCALYPTUS DELEGATENSIS
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The major components of a dichloromethane extract of mature Eucalyptus delegatensis leaves were cis- and trans-p-2-menthen-1-ol, trans-piperitol, α- and β-eudesmol, 4-phenyl-2-butanone and methyl cinnamate.The major terpenoid was considered to be trans-piperitol, which was responsible for the peppermint aroma of freshly crushed leaves.The steam distillate of the same leaves contained the above compounds together with a number of monoterpene hydrocarbons which were considered to be artefacts.Use of these hydrocarbons as chemotaxonomic markers was considered to be erroneous.Key Word Index-Eucalyptus delegatensis; Myrtaceae; alpine ash; essential oil; cis- and trans-p-2-menthen-1-ol; trans-piperitol; monoterpenoids; sesquiterpenoids; phenylpropanoids; peppermint aroma; chemotaxonomy.
- Weston, Roderick J.
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p. 1943 - 1946
(2007/10/02)
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- Lanthanoids in Organic Synthesis. 6. The Reduction of α-Enones by Sodium Borohydride in the Presence of Lanthanoid Chlorides: Synthetic and Mechanistic Aspects
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Lanthanoid chlorides (LnCl3) are efficient catalysts for the regioselective 1,2-reduction of α-enones by NaBH4 in methanol solution.Optimal conditions of this reaction have been determined.A mechanistic interpretation depicting the role of the Ln3+ ions is given.The major effect of Ln3+ is the catalysis of BH4- decomposition by the hydroxylic solvent to afford alkoxyborohydrides, which may be responsible for the observed regioselectivity.The stereoselectivity of the process is also modified by the presence of the Ln3+ ions, in that axial attack of cyclohexanone systems is enhanced.
- Gemal, Andre L.,Luche, Jean-Louis
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p. 5454 - 5459
(2007/10/02)
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- SYNTHESIS OF 1,2,3-TRIHYDROXY-p-MENTHANES
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Seven new stereoisomers of 1,2,3-trihydroxy-p-menthane have been synthesised.Their stereochemistry, proved mainly via chemical transformations and confirmed by (1)H-NMR, is discussed.
- Baragliu, A.,Grandolini, G.,Rossi, C.,Casinovi, C. G.
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p. 645 - 649
(2007/10/02)
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