- Synthesis of Helical Quinone Derivatives by Oxidative Coupling of Substituted 2-Hydroxybenzo[c]phenanthrenes
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A concise synthesis of novel substituted quinone derivatives from commercially available starting materials was developed. For this synthesis, classical photo-induced 6π-electrocyclization was utilized, followed by oxidative aromatization reaction, and su
- Shahabuddin, Mohammad,Akutsu, Akira,Kimura, Takao,Karikomi, Michinori
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- Tandem Acceptorless Dehydrogenative Coupling-Decyanation under Nickel Catalysis
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The development of new catalytic processes based on abundantly available starting materials by cheap metals is always a fascinating task and marks an important transition in the chemical industry. Herein, a nickel-catalyzed acceptorless dehydrogenative coupling of alcohols with nitriles followed by decyanation of nitriles to access diversely substituted olefins is reported. This unprecedented C=C bond-forming methodology takes place in a tandem manner with the formation of formamide as a sole byproduct. The significant advantages of this strategy are the low-cost nickel catalyst, good functional group compatibility (ether, thioether, halo, cyano, ester, amino, N/O/S heterocycles; 43 examples), synthetic convenience, and high reaction selectivity and efficiency.
- Babu, Reshma,Balaraman, Ekambaram,Midya, Siba P.,Subaramanian, Murugan,Yadav, Vinita
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p. 7552 - 7562
(2021/06/28)
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- Stereospecific Iron-Catalyzed Carbon (sp2)-Carbon (sp2) Cross-Coupling of Aryllithium with Vinyl Halides
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We present herein an efficient synthetic protocol involving iron-catalyzed cross-coupling of organolithium compounds with vinyl halides as key coupling partners. More than 30 examples were obtained with moderate to good yields and high stereoselectivities. The practicality of this method is evidenced by a gram-scale synthesis. In addition, a preliminary mechanistic investigation was also performed.
- Chen, Peng,Peng, Xiao-Shui,Wang, Zhi-Yong,Wong, Henry N. C.
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supporting information
p. 4385 - 4390
(2021/06/27)
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- Novel Carbazole-Based N-Heterocyclic Carbene Ligands to Access Synthetically Relevant Stilbenes in Pd-Catalyzed Coupling Processes
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A series of new carbazole-based N-heterocyclic carbene (NHC) ligands have been synthesized in a simple and facile synthetic route and subsequently used in a Pd/carbazole-based NHC catalytic system, which was found to be effective in catalyzing Heck reactions to provide substituted stilbene derivatives in good yields. Several bioactive stilbenes, including pterostilbene, pinosylvin, trimethoxy resveratrol, and resveratrol, were synthesized in good yields, and a 10 mmol scale-up was also performed for trimethoxy resveratrol. The synthetic application was also extended by performing a double-tandem chemoselective Heck reaction followed by Miyaura borylation in a one-pot procedure to give single-step access to synthetically useful stilbenyl boronate esters. Similarly, a unique triple-tandem protocol of a chemoselective Heck reaction/Miyaura borylation/Suzuki–Miyaura coupling reaction sequence was performed for the one-pot modification of biologically relevant molecules.
- Girase, Tejpalsingh Ramsingh,Kapdi, Anant R.
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supporting information
p. 2611 - 2619
(2019/07/05)
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- Model Guided Development of a Simple Catalytic Method for the Synthesis of Unsymmetrical Stilbenes by Sequential Heck Reactions of Aryl Bromides with Ethylene
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Stilbenes are important and useful structural moieties, but methods for their preparation typically possess numerous inefficiencies. Presented here is a methodology for the two-step, one pot preparation of unsymmetrical stilbenes via sequential Heck reactions. The first Heck reaction with ethylene gas was analysed as a function of temperature and pressure for electronically differentiated naphthyl bromides and model-aided reaction optimization was utilized to define the system. In addition, reactNMR was utilized to determine ethylene solubility in common organic solvents useful for Heck reactions. Finally, an optimized sequential Heck reaction process was developed and applied to a range of substrates allowing for efficient preparation of unsymmetrical stilbenes, including the natural antioxidant, pterostilbene. (Figure presented.).
- Barlow, Helen,Buser, Jonas Y.,Glauninger, Hendrik,Luciani, Carla V.,Martinelli, Joseph R.,Oram, Niall,Thompson-Van Hook, Nichole,Richardson, Jeffery
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p. 2678 - 2690
(2018/06/04)
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- Nickel-catalyzed synthesis of (E)-olefins from benzylic alcohol derivatives and arylacetonitriles via C-O activation
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An efficient Ni-catalyzed synthesis of (E)-olefins using the readily available benzylic alcohol derivatives and arylacetonitriles is described. This transformation should proceed via a tandem process involving nickel-catalyzed cross coupling via C-O activation and subsequent stereoselective E2 elimination.
- Xiao, Jing,Yang, Jia,Chen, Tieqiao,Han, Li-Biao
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p. 2157 - 2160
(2016/02/05)
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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 37; 48-49; 54
(2015/06/18)
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- Asymmetric catalysis on the nanoscale: The organocatalytic approach to helicenes
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The first asymmetric organocatalytic synthesis of helicenes is reported. A novel SPINOL-derived phosphoric acid, bearing extended π-substituents, catalyzes the asymmetric synthesis of helicenes through an enantioselective Fischer indole reaction. A variety of azahelicenes and diazahelicenes could be obtained with good to excellent yields and enantioselectivities. Twisting indoles: A novel chiral Bronsted acid, specifically designed for long-range control on a nanoscale, catalyzes the asymmetric synthesis of azahelicenes through a Fischer indolization. The method has the advantage of starting from simple achiral starting materials, which can be modified by changing the protecting group (R2) or the terminal substituents (R1, R3). The products can be further oxidized to polyaromatic systems.
- Koetzner, Lisa,Webber, Matthew J.,Martinez, Alberto,Defusco, Claudia,List, Benjamin
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supporting information
p. 5202 - 5205
(2014/05/20)
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- N,N′-Mono substituted acyclic thioureas: Efficient ligands for the palladium catalyzed Heck reaction of deactivated aryl bromides
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A series of N,N′-mono substituted acyclic thiourea ligands are found to be highly active phosphine-free catalysts for palladium catalyzed Heck reaction of aryl iodides and bromides with olefins. We have achieved high turnover numbers for aryl iodides with olefins (TONs up to 970,000 for the reaction of iodobenzene with styrene).
- Keesara, Srinivas,Parvathaneni, Saiprathima,Mandapati, Mohan Rao
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p. 6769 - 6772
(2015/05/05)
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- Palladium nanoparticles in glycerol: A versatile catalytic system for C-X bond formation and hydrogenation processes
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Palladium nanoparticles stabilised by tris(3-sulfophenyl)phosphine trisodium salt in neat glycerol have been synthesised and fully characterised, starting from both Pd(II) and Pd(0) species. The versatility of this innovative catalytic colloidal solution has been proved by its efficient application in C-X bond formation processes (X=C, N, P, S) and C-C multiple bond hydrogenation reactions. The catalytic glycerol phase could be recycled more than ten times, preserving its activity and selectivity. The scope of each of these processes has demonstrated the power of the as-prepared catalyst, isolating the corresponding expected products in yields higher than 90%. The dual catalytic behaviour of this glycerol phase, associated to the metallic nanocatalysts used in wet medium (molecular- and surface-like behaviour), has allowed attractive applications in one-pot multi-step transformations catalysed by palladium, such as C-C coupling followed by hydrogenation, without isolation of intermediates using only one catalytic precursor. Copyright
- Chahdoura, Faouzi,Pradel, Christian,Gomez, Montserrat
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supporting information
p. 3648 - 3660
(2014/01/06)
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- Single electron transfer-induced cross-coupling reaction of alkenyl halides with aryl Grignard reagents
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Alkenyl halides were found to undergo coupling with aryl Grignard reagents to give the corresponding styrene derivatives in a stereo-retained manner. The cross-coupling reaction is considered to proceed through a single electron transfer mechanism.
- Shirakawa, Eiji,Watabe, Ryo,Murakami, Takuya,Hayashi, Tamio
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supporting information
p. 5219 - 5221
(2013/06/27)
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- Continuous flow photocyclization of stilbenes-scalable synthesis of functionalized phenanthrenes and helicenes
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A continuous flow oxidative photocyclization of stilbene derivatives has been developed which allows the scalable synthesis of backbone functionalized phenanthrenes and helicenes of various sizes in good yields.
- Lefebvre, Quentin,Jentsch, Marc,Rueping, Magnus
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supporting information
p. 1883 - 1890
(2013/10/22)
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- ONE POT MULTICOMPONENT SYNTHESIS OF SOME NOVEL HYDROXY STILBENE DERIVATIVES WITH ALPHA, BETA-CARBONYL CONJUGATION UNDER MICROWAVE IRRADIATION
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The present invention provides a method for the preparation of some novel multiconjugated 2- or 4-hydroxy substituted stilbenes. The method provides one pot multicomponent approach wherein 3-4 step reaction sequences viz. condensation, decarboxylation and Heck coupling occur simultaneously which results in an enhanced yield of desired products and reduced reaction times
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Page/Page column 8
(2012/07/13)
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- Cu(acac)2-catalyzed synthesis of functionalized bis(arylmethyl)zinc reagents and their olefination reaction with aromatic aldehydes
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An efficient and facile copper(II) acetylacetonate catalyzed synthesis of functionalized bis(arylmethyl)zinc reagents from arylmethyl halides and their olefination reaction with aromatic aldehydes is reported. Aluminum trichloride was found to be the key ingredient in these reactions and (E)-stilbenes were obtained in high yields. Georg Thieme Verlag Stuttgart · New York.
- Fu, Ying,Hu, Xuemei,Chen, Yaojuan,Yang, Yanshou,Hou, Hongxia,Hu, Yulai
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experimental part
p. 1030 - 1036
(2012/05/04)
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- Palladium-catalyzed dehydrative Heck olefination of secondary aryl alcohols in ionic liquids: Towards a waste-free strategy for tandem synthesis of stilbenoids
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All in one: A tandem strategy has been developed wherein secondary aryl alcohols are directly coupled with aryl halides to provide stilbenoids through a dehydrative Heck sequence in the ionic liquid [hmim]Br, and with water as a by-product under microwave irradiation (see scheme). Classical methods do not permit this sequence to proceed in one pot, and some methods require multiple steps. hmim=1-n-hexyl-3-methylimidazolium. Copyright
- Kumar, Rakesh,Shard, Amit,Bharti, Richa,Thopate, Yogesh,Sinha, Arun Kumar
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scheme or table
p. 2636 - 2639
(2012/04/17)
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- Nickel(0)-catalyzed heck cross-coupling via activation of aryl C-OPiv bonds
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Using a Ni(dppf) catalyst generated in situ, Heck cross-coupling of aryl pivalates with a variety of olefin partners has been accomplished. This method represents one of the first examples of a C-C cross-coupling via activation of a strong C-O bond with a
- Ehle, Andrew R.,Zhou, Qi,Watson, Mary P.
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p. 1202 - 1205
(2012/05/04)
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- One-pot synthesis of stilbenes by dehydrohalogenation-Heck olefination and multicomponent Wittig-Heck reaction
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A variant of olefination reaction involving in situ generation of styrene by either one-pot dehydrohalogenation-Heck or one-pot multicomponent Wittig-Heck reaction is developed.
- Saiyed, Akeel S.,Bedekar, Ashutosh V.
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experimental part
p. 6227 - 6231
(2011/01/04)
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- Carbon - Carbon formation via Ni-catalyzed suzuki - Miyaura coupling through C - CN bond cleavage of aryl nitrile
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The Suzuki-Miyaura coupling of aryl nitriles with aryl/alkenyl boronic esters is reported. With this method, the cyano group could be applied as a protecting group of arenes and finally as a leaving group to further construct polyaryl scaffolds.
- Yu, Da-Gang,Yu, Miao,Guan, Bing-Tao,Li, Bi-Jie,Zheng, Yang,Wu, Zhen-Hua,Shi, Zhang-Jie
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supporting information; scheme or table
p. 3374 - 3377
(2009/12/01)
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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 22
(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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- Further naphthylcombretastatins. An investigation on the role of the naphthalene moiety
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By synthesis and biological studies of new naphthalene analogues of combretastatins, we have found that the naphthalene is a good surrogate for the isovanillin moiety (3-hydroxy-4-methoxyphenyl) of combretastatin A-4, always generating highly cytotoxic analogues when combined with the 3,4,5-trimethoxyphenyl or related systems. On the other hand, when the naphthalene replaces the 3,4,5-trimethoxyphenyl moiety, the cytotoxic activity is largely decreased. The most cytotoxic naphthalene analogues of combretastatins, which also produce inhibition of tubulin polymerization, exerted their antimitotic effects through microtubule network disruption and subsequent G2/M arrest of the cell cycle in human cancer cells.
- Maya, Ana B. S.,Pérez-Melero, Concepción,Mateo, Carmen,Alonso, Dulce,Fernández, José Luis,Gajate, Consuelo,Mollinedo, Faustino,Peláez, Rafael,Caballero, Esther,Medarde, Manuel
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p. 556 - 568
(2007/10/03)
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- Palladium-Imidazolium Carbene Catalyzed Mizoroki-Heck Coupling with Aryl Diazonium Ions
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(Matrix Presented) Catalyst formed from N,N-bis(2,6-diisopropylphenyl)dihydroimidazolium chloride and palladium(II) acetate (2 mol %) was used, without added base, to efficiently produce Heck coupled products with olefins and aryl diazonium tetrafluoroborate substrates. The reactions were performed at room temperature, giving product in 2-4 h with 80-90% yields for isolated materials. Diazonium ions, formed in situ directly from anilines, also couple under these conditions.
- Andrus, Merritt B.,Song, Chun,Zhang, Jiuqing
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p. 2079 - 2082
(2007/10/03)
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- A new general route to 1,2-diarylethylenes, 1,4-diarylbutadienes and 1,6-diarylhexatrienes through cycloaromatization of β-oxodithioacetals
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A new general route for the title olefins 5 a-e, 12, 13, 8a-e and 11 a-e has been developed through nucleophilic addition of respective Grignard reagents i.e. allyl-, benzyl-, 1-(naphthylmethyl) magnesium halides to 5-aryl-1,1-bis(methylthio)pent-4-en-3-ones, 7-aryl-1,1-bis(methylthio)hepta-4,6-dien-3-ones and 9-phenyl-1,lbis(methylthio)nona-4,6,8-trien-3-one followed by cycloaromatization of the resulting 3-substituted 1,1-bis(methylthio)alken-3-ols in the presence of boron trifluoride-diethyl ether complex.
- Rao,Singh,Ila,Junjappa
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p. 1075 - 1077
(2007/10/02)
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- Arylation of Alkenyl Bromides Catalysed by Platinum Complexes
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Biphosphine platinum complexes catalyse the cross-coupling of arylmagnesium halides and arylethenyl bromides under mild conditions.
- Brown, John M.,Cooley, Neil A.,Price, David W.
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p. 458 - 460
(2007/10/02)
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