- Method for synthesizing spiro compound of dihydro-1H-indene
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The invention provides a method for synthesizing a spiro compound 1 of dihydro-1H-indene. The method comprises the following steps: 1) reacting 3-methoxybenzaldehyde with carbethoxyethylidene triphenylphosphorane 2 in a halohydrocarbon solvent at room temperature to obtain a compound 3; 2) hydrogenating the compound 3 in an alcohol solvent in the presence of a catalyst to obtain a compound 4; 3) reacting the compound 4 with liquid bromine in a halohydrocarbon solvent to obtain a compound 5; 4) reacting the compound 5 with N-vinyl-2-pyrrolidone in an ether solvent in the presence of a strong alkali to obtain a compound 6; 5) refluxing the compound 6 in an aqueous diluted acid solution to perform a rearrangement reaction in order to obtain a compound 7; and 6) performing a cyclization reaction on the compound 7 in anhydrous toluene in the presence of butyl lithium at an appropriate temperature to obtain the compound 1. The method has the advantages of initiative synthesis route, ingenious design idea, easily available and cheap starting materials, mild synthesis process conditions in every step, easiness in industrial production, high yield of every step, and high overall yield of the product.
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Paragraph 0031; 0032
(2018/09/20)
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- Chemo- and Regioselective Hydrogenolysis of Diaryl Ether C-O Bonds by a Robust Heterogeneous Ni/C Catalyst: Applications to the Cleavage of Complex Lignin-Related Fragments
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We report the chemo- and regioselective hydrogenolysis of the C-O bonds in di-ortho-substituted diaryl ethers under the catalysis of a supported nickel catalyst. The catalyst comprises heterogeneous nickel particles supported on activated carbon and furnishes arenes and phenols in high yields without hydrogenation. The high thermal stability of the embedded metal particles allows C-O bond cleavage to occur in highly substituted diaryl ether units akin to those in lignin. Preliminary mechanistic experiments show that this catalyst undergoes sintering less readily than previously reported catalyst particles that form from a solution of [Ni(cod)2].
- Gao, Fang,Webb, Jonathan D.,Hartwig, John F.
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p. 1474 - 1478
(2016/02/12)
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- Structure activity relationship of brevenal hydrazide derivatives
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Brevenal is a ladder frame polyether produced by the dinoflagellate Karenia brevis. This organism is also responsible for the production of the neurotoxic compounds known as brevetoxins. Ingestion or inhalation of the brevetoxins leads to adverse effects such as gastrointestinal maladies and bronchoconstriction. Brevenal shows antagonistic behavior to the brevetoxins and shows beneficial attributes when administered alone. For example, in an asthmatic sheep model, brevenal has been shown to increase tracheal mucosal velocity, an attribute which has led to its development as a potential treatment for Cystic Fibrosis. The mechanism of action of brevenal is poorly understood and the exact binding site has not been elucidated. In an attempt to further understand the mechanism of action of brevenal and potentially develop a second generation drug candidate, a series of brevenal derivatives were prepared through modification of the aldehyde moiety. These derivatives include aliphatic, aromatic and heteroaromatic hydrazide derivatives. The brevenal derivatives were tested using in vitro synaptosome binding assays to determine the ability of the compounds to displace brevetoxin and brevenal from their native receptors. A sheep inhalation model was used to determine if instillation of the brevenal derivatives resulted in bronchoconstriction. Only small modifications were tolerated, with larger moieties leading to loss of affinity for the brevenal receptor and bronchoconstriction in the sheep model.
- Goodman, Allan,McCall, Jennifer R.,Jacocks, Henry M.,Thompson, Alysha,Baden, Daniel,Abraham, William M.,Bourdelais, Andrea
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p. 1839 - 1858
(2014/06/09)
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- GPBP inhibition using Q2 peptidomimetics
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Disclosed are compounds of formula: that inhibiting GPBP activity, making them useful as therapeutics in antibody-mediated disorders, drug-resistant cancer, inflammation, protein misfolding and ER stress-mediated disorders, and aberrant apoptosis.
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Page/Page column 35
(2011/05/08)
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- Tandem β-boration/arylation of α,β-unsaturated carbonyl compounds by using a single palladium complex to catalyse both steps
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Diphenyl(3-methyl-2-indolyl)phosphine (C9H8NPPh 2, 1) gives stable dimeric palladium(II) complexes that contain the phosphine in P,Nbridging coordination mode. On treating 1 with [Pd(O 2CCH3)2], the new complexes [Pd(μ-C 9H7NPPh2)-(NCCH3)]2 (2) or [Pd(μ-C9H7NPPh2)-(μ-O 2CCH3)]2 (3) were isolated, depending on the solvent used, acetonitrile or toluene, respectively. Further reaction of 3 with the ammonium salt of 1 led to the substitution of one carboxylate ligand to afford [Pd(u-C9H7NPPh2)3(μ-O 2CCH3)] (4), in which the bimetallic unit is bonded by three C9H7NPPh2- moieties and one carboxylate group. Using this methodology, [Pd2(μ-C 6H4PPh2)2(μ-C9H 7NPPh2)(μ-O2CCX3)] (X = H (7); J. = F (8)) were synthesised from the ortho-metalated compounds [Pd(C 6H4PPh2)(μO2CCX3)], (X = H (5); J. = F (6)). Complexes 3, 4, 7, and 8 have been found to be active in the catalytic β-boration of α,β-unsaturated esters and ketones under mild reaction conditions. Hindrance of the carbonyl moiety has an influence on the reaction rate, but quantitative conversion was achieved in many cases. More remarkably, when aryl bromides were added to the reaction media, complex 7 induced a highly successful consecutive β-boration/crosscoupling reaction with dimethyl acrylamide as the substrate (99% conversion, 89 % isolated yield).
- Bonet, Amadeu,Gulyas, Henrik,Koshevoy, Igor O.,Estevan, Francisco,Sanau, Mercedes,Ubeda, M. Angeles,Fernandez, Elena
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supporting information; experimental part
p. 6382 - 6390
(2010/08/03)
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- CoBr2(Bpy): An efficient catalyst for the direct conjugate addition of aryl halides or triflates onto activated olefins
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An efficient cobalt-catalyzed method devoted to the direct conjugate addition of functionalized aryl compounds onto Michael acceptors is described. The CoBr2(2,2′-bipyridine) complex appears to be an extremely suitable catalyst for the activation of a variety of aromatic reagents ranging from halides to triflates functionalized by reactive groups. This procedure allows for the synthesis of compounds resulting from 1,4-addition in good to excellent yields. The versatility of this original process represents a simple alternative to most known methods using organometallic reagents.
- Amatore, Muriel,Gosmini, Corinne,Perichon, Jacques
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p. 6130 - 6134
(2007/10/03)
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- 3-arylpropanoate esters through the palladium-catalyzed reaction of aryl halides with acrolein diethyl acetal
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The reaction of aryl halides with acrolein diethyl acetal in the presence of Pd(OAc)2, n-Bu3N, and n-Bu4NCl in DMF at 90°C affords ethyl 3-arylpropanoates. A variety of functional groups are tolerated in the aryl halides, including ether, aldehyde, ketone, ester, nitrile, and nitro groups. ortho-Substituents do not hamper the reaction. 3-Arylpropanoate esters were isolated in good to excellent yields with many neutral, electron-rich and electron-poor aryl iodides and electron-poor aryl bromide. Neutral and electron-rich aryl bromides gave the desired ester in moderate yields.
- Battistuzzi, Gianfranco,Cacchi, Sandro,Fabrizi, Giancarlo,Bernini, Roberta
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p. 1133 - 1136
(2007/10/03)
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- Inhibition of uridine phosphorylase: Synthesis and structure-activity relationships of aryl-substituted 5-benzyluracils and 1-[(2- hydroxyethoxy)methyl]-5-benzyluracils
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A series of 1-[(2-hydroxyethoxy)methyl]-5-benzyluracils were synthesized and tested for inhibition of murine liver uridine phosphorylase (UrdPase). Inhibitors of UrdPase are reported to enhance the chemotherapeutic utility of 5-fluoro-2'-deoxyuridine and 5-fluorouracil and to ameliorate zidovudine- induced anemia in animal models. We prepared a series of 5-aryl-substituted analogues of 5-benzylacyclouridine (BAU), a good inhibitor of UrdPase (IC50 of 0.46 μM), to develop a compound with enhanced potency and improved pharmacokinetics. The first phase of structure-activity relationship studies on a series of 32 aryl-substituted 5-benzyluracils found several 5-(3- alkoxybenzyl) analogues of 5-benzyluracil with enhanced potency. The acyclovir side chain, the (2-hydroxyethoxy)methyl group, was substituted on the more potent aryl-substituted 5-benzyluracils. The two most potent compounds, 10y (3-propoxy) and 10dd (3-sec-butoxy), were inhibitors of UrdPase with IC50s of 0.047 and 0.027 μM, respectively. Six compounds were tested in vivo for effects on steady-state concentrations of circulating uridine in rats. Plasma uridine levels were elevated 3-9-fold by compound levels that ranged from 8 to 50 μM.
- Orr,Musso,Boswell,Kelley,Joyner,Davis,Baccanari
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p. 3850 - 3856
(2007/10/02)
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- A NOVEL METHOD FOR CARBON-CARBON BOND FORMATION PALLADIUM-CATALYZED CROSS-COUPLING REACTION OF PHENYL FLUOROALKANESULFONATES WITH ORGANOZINC REAGENTS
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Cross-coupling reaction of phenyl fluoroalkanesulfonates with three kinds of organozinc reagents in the presence of palladium gives the corresponding alkylbenzenes in good yields.A possible mechanism is suggested.
- Chen, Qing-Yun,He, Ya-Bo
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p. 2387 - 2388
(2007/10/02)
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