- Room-Temperature meta-Functionalization: Pd(II)-Catalyzed Synthesis of 1,3,5-Trialkenyl Arene and meta-Hydroxylated Olefin
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Development of meta-C-H functionalization reactions at room temperature continues to be a tough challenge. Use of a phosphonate linkage allowed a Pd (II)-catalyzed meta-C-H functionalization at room temperature while incorporating a cyanophenol-based dire
- Bera, Milan,Sahoo, Santosh K.,Maiti, Debabrata
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- Method for synthesizing trans-olefin compound
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The invention discloses a trans-olefin compound synthesis method, which comprises: carrying out a heating reaction on an alkyne compound represented by a general formula (I), a reducing agent and a solvent to obtain a trans-olefin compound represented by a general formula (II), wherein the synthesis route is as follows: R1 and R2 are independently selected from hydrogen, alkyl, cycloalkyl or aryl;wherein the reducing agent is a sulfur-containing compound and is selected from at least one of thioacetamide, N,N-dimethyl dithiocarbamate dimethyl ammonium salt, dimethyl amino sodium dithioformatedihydrate, potassium ethyl xanthate and potassium isopropyl xanthate. According to the method, a cheap, efficient and safe reducing agent is utilized to realize high-selectivity reduction of alkyne to prepare trans-olefin under the condition of no transition metal catalysis, so that the method is simple and easy to implement, wide in substrate application range and easy to realize industrialization.
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Paragraph 0075-0078
(2020/06/20)
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- Galloyl esters of trans-stilbenes are inhibitors of FASN with anticancer activity on non-small cell lung cancer cells
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Fatty acid synthase (FASN) is a lipogenic enzyme that is selectively upregulated in malignant cells. There is growing consensus on the oncogenicity of FASN-driven lipogenesis and the potential of FASN as a druggable target in cancer. Here, we report the synthesis and FASN inhibitory activities of two novel galloyl esters of trans-stilbene EC1 and EC5. Inhibition of FASN was accompanied by a loss in AKT activation and profound apoptosis in several non-small cell lung cancer (NSCLC) cells at the growth inhibitory concentrations of EC1 and EC5. Both FASN and phospho-AKT levels were concurrently downregulated. However, addition of a lipid concentrate to the treated cells reinstated cell viability and reversed the loss of FASN and AKT protein levels, thus recapitulating the causal relationship between FASN inhibition and the loss in cell viability.
- Tan, Yu-Jia,Ali,Tee, Sheng-Yang,Teo, Jun-Ting,Xi, Yu,Go, Mei-Lin,Lam
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- Xanthate-mediated synthesis of (E)-alkenes by semi-hydrogenation of alkynes using water as the hydrogen donor
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Semi-hydrogenation of alkynes is one of the most widely used methods for obtaining alkenes in laboratory preparation and in industry. Transition metal catalysts have been extensively studied for this transformation, but the tolerance of functional groups, such as pyridine,-OH,-NH2,-Bpin, and halides, and the toxicity of the trace amount of transition metal catalysts are still highly challenging. In this study, we report a general and robust strategy to achieve the semi-hydrogenation of alkynes using inexpensive and commercially available xanthate as the mediator. Mechanism studies support a non-radical process and H2O acts as the hydrogen donor.
- Luo, Xianglin,Chen, Xiuwen,Chen, Lu,Zhang, Kun,Li, Yibiao
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supporting information
p. 2170 - 2173
(2019/02/24)
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- Regioselective Hydroxylation of Stilbenes by Engineered Cytochrome P450 from Thermobifida fusca YX
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Since the past decades, the plant stilbenoid resveratrol has gained significant attention of the general public as well as the research community due to its versatile medicinal properties. Apart from resveratrol, there is also an increasing interest in other plant stilbenoids because of their different potential biological activities. In order to meet the increasing demand for stilbenoids, alternative and sustainable approaches for their production are needed. We identified the cytochrome P450 monooxygenase 154E1 from Thermobifida fusca YX (CYP154E1) which enables the synthesis of (E)-4,4′-dihydroxystilbene via direct double hydroxylation of (E)-stilbene. The construction of a triple mutant led to a more than six-fold increased catalytic efficiency compared to the wild type enzyme. CYP154E1 and variants thereof accepted not only (E)-stilbene but also possessed remarkable activity towards ortho- and meta-substituted hydroxystilbenes leading to resveratrol, (E)-2,4′-dihydroxystilbene, (E)-2,4′,5-trihydroxystilbene and (E)-3,4′-dihydroxystilbene. The combination of protein engineering and the use of methyl-β-cyclodextrin as substrate solubilizing agent resulted in product titers of up to 4.2 g L?1 and enzyme total turnover numbers (TTN) of up to 20,000. (Figure presented.).
- Rühlmann, Ansgar,Antovic, Dragutin,Müller, Thomas J. J.,Urlacher, Vlada B.
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p. 984 - 994
(2017/03/27)
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- Tetrahydropyrrolization of Resveratrol and Other Stilbenes Improves Inhibitory Effects on DNA Oxidation
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The inhibitory effect of resveratrol on DNA oxidation caused by 2,2′-azobis(2-amidinopropane hydrochloride) (AAPH) was found to be enhanced if the C=C bond in resveratrol was converted into tetrahydropyrrole by reaction with azomethine ylide (CH2=N+(CH3)CH2?). This encouraged us to explore whether the inhibitory activities of other stilbenes could also be increased by the same method. We found that the inhibitory effects of the tetrahydropyrrole derivatives on AAPH-induced oxidation of DNA were higher than those of the corresponding stilbenes, because the tetrahydropyrrole motif can provide hydrogen atoms to be abstracted by radicals. Therefore, the tetrahydropyrrolization offered an advantage for enhancing the antioxidant effects of stilbenes. Notably, (CH3)3SiCH2N(CH3)CH2OCH3(in the presence of CF3COOH) and (CH3)3NO (in the presence of LiN(iPr)2) can be used to generate azomethine ylide for the tetrahydropyrrolization of stilbenes containing electron-withdrawing and -donating groups, respectively.
- Bao, Liang-Liang,Liu, Zai-Qun
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p. 1617 - 1625
(2016/08/28)
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- Cyclodextrin-Grafted Silica-Supported Pd Nanoparticles: An Efficient and Versatile Catalyst for Ligand-Free C-C Coupling and Hydrogenation
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Silica is an extremely versatile support, which is capable of hosting metal nanoparticles (NPs) and enhancing their stability and reactivity. In this study, a novel cyclodextrin/silica support for Pd NPs, which we have denoted Pd/Si-CD, has been prepared. The highly efficient and homogeneous impregnation of small palladium nanoparticles on this support has been carried out under conventional conditions, and ultrasound irradiation has been shown to have a beneficial effect on catalyst preparation. The catalyst exhibited excellent activity in ligand-free C-C Suzuki and Heck couplings with a large number of aryl iodide and bromides, in which microwave irradiation use cuts down reaction time. Pd/Si-CD have shown high activity and selectivity in the hydrogenation reaction, and the semihydrogenation of phenyl acetylene was also studied with excellent results.
- Martina, Katia,Baricco, Francesca,Caporaso, Marina,Berlier, Gloria,Cravotto, Giancarlo
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p. 1176 - 1184
(2016/04/05)
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- THERAPEUTIC AGENTS FOR SKIN DISEASES AND CONDITIONS
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The present invention relates to method(s) of treating a subject afflicted with a skin disease or condition, the method comprising administering to the subject or patient in need a composition comprising a therapeutically effective amount of a substituted cis or trans- stilbene or a stilbene hybrid. A method of treating or reducing the likelihood of a skin disease or condition in a patient is an additional embodiment of the present invention. Preferred pharmaceutical compositions of the invention include nanoemulsions comprising a therapeutically effective amount of a substituted cis or trans-stilbene or stilbene hybrid and at least one antibiotic.
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Page/Page column 36; 48-49; 52
(2015/06/18)
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- Inhibition of VEGF expression in cancer cells and endothelial cell differentiation by synthetic stilbene derivatives
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We here report the synthesis of several stilbene derivatives. They show a measurable inhibitory effect on angiogenesis, some of them to a higher degree than resveratrol. Test methods included cell proliferation and tube formation assays using bovine aorta endothelial cells. In addition, it has been confirmed through the reverse transcriptase/polymerase chain reaction experiment that these stilbene derivatives downregulate the expression of the gene related to the production of the angiogenesis factor VEGF in cancer cells.
- Martí-Centelles, Rosa,Cejudo-Marín, Rocío,Falomir, Eva,Murga, Juan,Carda, Miguel,Alberto Marco
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p. 3010 - 3015
(2013/07/05)
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- A robust first-pass protocol for the heck-mizoroki reaction
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The Heck-Mizoroki (HM) reaction is one of the most widely used C-C bond-forming methods of contemporary synthesis. Notwithstanding this, these reactions frequently require significant optimization before efficient transformations can be obtained. We describe here the results of a study that aimed to establish a generic experimental protocol for HM reactions which enables acceptable yields from first-pass experiments. The methodology utilizes readily available stable catalysts and can be applied to a broad range of coupling partners.
- Murray, Paul M.,Bower, John F,Cox, David K,Galbraith, Ewan K,Parker, Jeremy S,Sweeney, Joseph B.
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p. 397 - 405
(2013/04/24)
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- MOLECULARLY IMPRINTED POLYMERS
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The present invention provides methods of designing molecularly imprinted polymers (MIPs) which have applications in extracting bioactive compounds from a range of bioprocessing feedstocks and wastes. The present invention is further directed to MIPs designed by the methods of the present invention.
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- Substituted CIS- and trans-stilbenes as therapeutic agents
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The present invention relates to method(s) of treating a subject afflicted with cancer or a precancerous condition, an inflammatory disease or condition, and/or stroke or other ischemic disease or condition, the method comprising administering to the subject or patient in need a composition comprising a therapeutically effective amount of a substituted cis or trans-stilbene.
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Page/Page column 21
(2010/11/28)
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- Substituted trans-stilbenes, including analogues of the natural product resveratrol, inhibit the human tumor necrosis factor alpha-induced activation of transcription factor nuclear factor kappaB
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The transcription factor nuclear factor kappaB (NF-κB), which regulates expression of numerous antiinflammatory genes as well as genes that promote development of the prosurvival, antiapoptotic state is up-regulated in many cancer cells. The natural product resveratrol, a polyphenolic trans-stilbene, has numerous biological activities and is a known inhibitor of activation of NF-κB, which may account for some of its biological activities. Resveratrol exhibits activity against a wide variety of cancer cells and has demonstrated activity as a cancer chemopreventive against all stages, i.e., initiation, promotion, and progression. The biological activities of resveratrol are often ascribed to its antioxidant activity. Both antioxidant activity and biological activities of analogues of resveratrol depend upon the number and location of the hydroxy groups. In the present study, phenolic analogues of resveratrol and a series of substituted trans-stilbenes without hydroxy groups were compared with resveratrol for their abilities to inhibit the human tumor necrosis factor alpha-induced (TNF-α) activation of NF-κB, using the Panomics NF-κB stable reporter cell line 293/NF-κB-luc. A series of 75 compounds was screened to identify substituted trans-stilbenes that were more active than resveratrol. Dose-response studies of the most active compounds were carried out to obtain IC50 values. Numerous compounds were identified that were more active than resveratrol, including compounds that were devoid of hydroxy groups and were 100-fold more potent than resveratrol. The substituted trans-stilbenes that were potent inhibitors of the activation of NFκB generally did not exhibit antioxidant activity. The results from screening were confirmed using BV-2 microglial cells where resveratrol and analogues were shown to inhibit LPS-induced COX-2 expression.
- Heynekamp, Justin J.,Weber, Waylon M.,Hunsaker, Lucy A.,Gonzales, Amanda M.,Orlando, Robert A.,Deck, Lorraine M.,Vander Jagt, David L.
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p. 7182 - 7189
(2007/10/03)
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- Synthesis, antitumor evaluation, and apoptosis-inducing activity of hydroxylated (E)-stilbenes
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The parallel solution-phase synthesis of a series of 30 monohydroxylated (E)-stilbene analogues is described. In vitro screening revealed low micromolar activity (GI50) against the MDA MB 468 breast cancer cell line. Activity in MDA MB 468 cells correlated with the ability to induce apoptosis following drug treatment by the most potent agents in the series, e.g., 5dy and 5jy, an observation further reinforced by Annexin V-FITC analysis and fluorescence microscopy.
- Lion, Cedric J.,Matthews, Charles S.,Stevens, Malcolm F. G.,Westwell, Andrew D.
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p. 1292 - 1295
(2007/10/03)
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- Hydroxystilbene compounds used as microbicidal active substances
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The use of hydroxystilbene compounds of formula wherein A is a radical of formula ?or a radical of formula ?and R1, R2, R3, R4and R5are each independently of the others hydrogen, halogen, hydroxy, Cs
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- Cycloadditions of mesitonitrile oxide with hydroxy- and methoxy-substituted stilbenes. A directing hydrogen bonding model
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The regioselectivity of the reaction of mesitonitrile oxide with o-hydroxystilbene in favour of the 5-(2-hydroxyphenyl) isomer (regioisomeric ratio 5:1) is accounted by a directing hydrogen bonding model, while for reactions of the p-hydroxy- and p-methoxystilbene which show a 2:1 ratio between the 5- and 4-regioisomer, an electron-donor effect is invoked. These phenomena of regioselectivity are supported by semiempirical AM1 calculations.
- Corsaro, Antonino,Buemi, Giuseppe,Chiacchio, Ugo,Pistara, Venerando,Rescifina, Antonio
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p. 905 - 918
(2007/10/03)
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- Palladium-catalyzed arylation of styrene and acrylic acid in water
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Palladium-catalyzed arylations of styrene and acrylic acid are shown to occur in the presence of base (Na2CO3 or K2CO3) in pure water using simple palladium compounds as catalyst precursors.Keywords: Palladium; Catalysis; Water; Solvent; Aryl
- Bumagin, N. A.,Bykov, V. V.,Sukhomlinova, L. I.,Tolstaya, T. P.,Beletskaya, I. P.
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p. 259 - 262
(2007/10/02)
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- Palladium-Catalyzed Reactions of Acrylic Acid and Styrene with Aryl Halides in Water
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New convenient versions of the Heck reaction in water were proposed for preparation of substituted cinnamic acids and stilbene.Arylation of acrylic acid with aryl halides was effected with palladium PdX2 or palladium black as catalysts in the presence of Na2CO3.To arylate styrene in water it is necessary to use palladium complexes with tris(o-tolyl)phosphine ligands, K2CO3, and small amounts of Bu4NBr or DMF.
- Bumagin, N. A.,Bykov, V. V.,Beletskaya, I. P.
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p. 439 - 444
(2007/10/03)
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- Pest control chemicals against pine wood nematodes
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Disclosed are (1) pest control chemicals against the pine wood nematodes containing an extract from a pine tree with an organic solvent, (2) a repellent against the pine wood nematodes containing α-humulene or a mixture of α-humulene and β-bisabolene, (3) a repellent against the pine wood nematodes containing a mixture of α-pinene and calarene, (4) a nematicide against the pine wood nematodes containing methyl ferulate, (+)-pinoresinol or a mixture thereof, and (5) highly effective pest control chemicals against pine wood nematodes containing hydroxystilbenes or salts thereof which are prepared by synthesizing methoxystilbenes from benzyl phosphonates and methoxybenzaldehydes by a Wittig-Horner reaction, performing demethylation to obtain the hydroxystilbenes, and preparing the salts thereof by conventional methods if necessary.
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- Synthesis and nematocidal activity of hydroxystilbenes
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Various (E)-hydroxystilbenes were synthesized from (E)/(Z) mixtures of methoxystilbenes through a new (Z)-(E) isomerization method followed by demethylation. The nematocidal activity appears when methoxystilbenes are demethylated to hydroxystilbenes. For this activity, a hydroxy group at the C-2 or C-3 position is necessary. Thus, 2-hydroxy-, 3-hydroxy-, 2,6-dihydroxy-, 3,4-dihydroxy-, 3,5-dihydroxy-, 2,2'-dihydroxy-, 3,3'-dihydroxy-, 3,4'dihydroxy-, 2-hydroxy-4-methoxy-, 5-hydroxy-2-methoxy-, 2-hydroxy-6-methoxy-, 6-allyloxy-2-hydroxy-, 3-hydroxy-5-methoxy-, and 5-allyloxy-3-hydroxystilbenes showed rather potent nematocidal activity. The activity of 5-allyloxy-3-hydroxystilbene was the strongest [minimal lethal concentration (MLC) = 30 μM]. The activities of the (E) and (Z) isomers were comparable. The activities were also retained, though they were weaker, in the dihydro derivatives, hydroxybibenzyls.
- Ali,Kondo,Tsuda
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p. 1130 - 1136
(2007/10/02)
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- Syntheses and Platelet Aggregation Inhibitory and Antithrombotic Properties of ethyl>benzenes
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A series of ethyl>benzene derivatives were synthesized and evaluated for their ability to inhibit collagen-induced platelet aggregation in vitro and to protect experimantal thrombosis in mice.The results showed that the compounds were in vitro inhibitors of collagen-induced platelet aggregation.Most of them were also effective in the mouse antithrombotic assay.The compounds were found to be potent antagonists to S2 serotonergic receptor, and good correlation (r = 0.85) between their S2 serotonergic receptor antagonism and their potency as platelet antiaggregatory drugs was observed.Among the compounds studied, monophenoxy>methyl>ethyl>succinate hydrochloride (12b, MCI-9042) was selected for further pharmacological and toxicological evaluation.
- Kikumoto, Ryoji,Hara, Hiroto,Ninomiya, Kunihiro,Osakabe, Masanori,Sugano, Mamoru,et al.
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p. 1818 - 1823
(2007/10/02)
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- Substituted (ω-aminoalkoxy)stilbene derivatives as a new class of anticonvulsants
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A series of substituted (ω-aminoalkoxy)stilbene derivatives has been synthesized and screened for anticonvulsant activity. The effect of structural modification of these molecules on the activities has been systematically examined. Potent anticonvulsant activity was displayed by 2-[4-(4-methyl-1-piperazinyl)butoxy]stilbene and some 2-[4-(3-alkoxy-1-piperidino)butoxy]stilbene derivatives, as determined by maximal electroshock seizure (MES) and pentylenetetrazol-induced convulsion tests in mice. One of these derivatives exhibited more potent anti-MES activity than diphenylhydantoin and carbamazepine in further pharmacological tests in rats, and its therapeutic index was superior to those of two antiepileptic drugs.
- Kikumoto,Tobe,Fukami,Ninomiya,Egawa
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p. 645 - 649
(2007/10/02)
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