- cis-BIS(7-METHYLNAPHTH-1-YL)BIS(TRIPHENYLPHOSPHAN)PLATIN(II)
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From the reaction of cis-dichlorbis(triphenylphosphane)platinum(II) with the lithium compound obtained as the bromination product of 2-methylnaphthalene cis-bis(7-metyhylnaphth-1-yl)bis(triphenylphosphane)platinum(II) (6), has been isolated.The unexpected formation of 6 has been explained.
- Brune, Hans Albert,Schaefer, Wolfgang,Spohn, Karl-Heinz,Weisemann, Claus
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- Lewis acid-mediated carboxylation of fused aromatic compounds with carbon dioxide
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Direct and regioselective carboxylation of fused aromatic compounds with carbon dioxide is achieved with the aid of a Lewis acid. Thus, treatment of naphthalene, anthracene, and phenanthrene with carbon dioxide (3.0 MPa) in benzene at 40 °C in the presenc
- Suzuki, Yutaka,Hattori, Tetsutaro,Okuzawa, Tomohiro,Miyano, Sotaro
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- Controlling chemoselectivity in reactions of unprotected naphthalene-1-carboxylic acid with strong bases
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Whereas treatment of unprotected naphthalene-1-carboxylic acid with alkyllithiums (RLi) affords 1,4-addition products, the reaction with LTMP/Me3SiCl under in situ quench conditions provides the arylsilane arising out from the substitution of l
- Tilly, David,Castanet, Anne-Sophie,Mortier, Jacques
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- Palladium-Catalyzed ortho-C-H Methylation of Benzoic Acids
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A palladium-catalyzed methylation of C-H bonds of benzoic acids with di-tert-butyl peroxide as the methylating reagent under an external oxidant and ligand-free conditions has been achieved. The reaction is found to be directed by a weakly coordinating carboxyl group, offering a facile route for the synthesis of highly functionalized ortho-methyl benzoic acids.
- Lv, Weiwei,Wen, Si,Liu, Jing,Cheng, Guolin
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p. 9786 - 9791
(2019/08/26)
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- Site- and regio-selective incorporation of carbon dioxide into the C(sp2)Si bond of benzosilacyclobutenes
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A reaction of benzosilacyclobutenes with carbon dioxide is catalyzed by a nickel complex having an N-heterocyclic carbene ligand. Carbon dioxide inserts into the C(sp2)Si bond in a site- and regio-selective manner to form a carboncarbon bond, furnishing benzoic acid derivatives.
- Ishida, Naoki,Okumura, Shintaro,Murakami, Masahiro
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p. 570 - 572
(2018/04/12)
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- Iron-Catalyzed Ortho C-H Methylation of Aromatics Bearing a Simple Carbonyl Group with Methylaluminum and Tridentate Phosphine Ligand
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Iron-catalyzed C-H functionalization of aromatics has attracted widespread attention from chemists in recent years, while the requirement of an elaborate directing group on the substrate has so far hampered the use of simple aromatic carbonyl compounds such as benzoic acid and ketones, much reducing its synthetic utility. We describe here a combination of a mildly reactive methylaluminum reagent and a new tridentate phosphine ligand for metal catalysis, 4-(bis(2-(diphenylphosphanyl)phenyl)phosphanyl)-N,N-dimethylaniline (Me2N-TP), that allows us to convert an ortho C-H bond to a C-CH3 bond in aromatics and heteroaromatics bearing simple carbonyl groups under mild oxidative conditions. The reaction is powerful enough to methylate all four ortho C-H bonds in benzophenone. The reaction tolerates a variety of functional groups, such as boronic ester, halide, sulfide, heterocycles, and enolizable ketones.
- Shang, Rui,Ilies, Laurean,Nakamura, Eiichi
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supporting information
p. 10132 - 10135
(2016/08/31)
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- Direct Carboxylation of Aryl Tosylates by CO2 Catalyzed by in situ-Generated Ni0
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A novel Ni0-catalyzed carboxylation of aryl tosylates with carbon dioxide has been achieved under moderate temperatures and atmospheric pressure. In this procedure, the active Ni0 species is generated in situ by simply mixing the Ni0 precatalyst [NiBr2(bipy)] with an excess of manganese metal. This approach requires neither a glove-box nor the tedious preparation of sophisticated intermediate organometallic derivatives. This mild, convenient, and user-friendly process is successfully applied to the valorization of carbon dioxide and the synthesis of versatile reactants with broad tolerance of substituents.
- Rebih, Fatima,Andreini, Manuel,Moncomble, Aurlien,Harrison-Marchand, Anne,Maddaluno, Jacques,Durandetti, Muriel
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p. 3758 - 3763
(2016/03/08)
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- Aryllithiums with increasing steric crowding and lipophilicity prepared from chlorides in diethyl ether. the first directly prepared room-temperature-stable dilithioarenes
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A convenient procedure has been developed for the preparation of synthetically useful, room-temperature-stable aryllithiums starting from aryl chlorides and lithium metal. The method provides a route to aryllithiums which have previously not been accessible cleanly or could only be prepared by using more expensive starting materials.
- Screttas, Constantinos G.,Steele, Barry R.,Micha-Screttas, Maria,Heropoulos, Georgios A.
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supporting information
p. 5680 - 5683
(2013/01/15)
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- Direct carboxylation of arenes and halobenzenes with CO2 by the combined use of AlBr3 and R3SiCl
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The Lewis acid-mediated direct carboxylation of aromatic compounds with CO2 is efficiently promoted by the addition of silyl chlorides bearing three alkyl and/or aryl substituents in total on the silicon atom. Thus, toluene, xylenes, mesitylene, and some other alkylbenzenes are treated with a 1:1 mixture of AlBr3 and Ph3SiCl in neat substrates under CO2 pressure (3.0 MPa) at room temperature, to give the corresponding carboxylic acids in 60-97% yields, based on AlBr3. Polycyclic arenes, including naphthalene, phenanthrene, and biphenyl, are regioselectively carboxylated in 91-98% yields with the aid of 1 molar equiv of AlBr3 and Ph3SiCl in an appropriate solvent, chosen from benzene, chlorobenzene, and fluorobenzene. These solvents, as well as bromobenzene, resist carboxylation; however, they are also carboxylated in moderate yields when treated with a 1:5 mixture of AlBr3 and iPrSiCl at elevated temperatures. The FT-IR spectrum of a mixture prepared by exposing a suspension of AlBr3 and Ph3SiCl in cyclohexane to CO 2 exhibits an absorption band around 1650 cm-1, assigned to the C=O stretching vibration of a species consisting of CO2, AlBr3, and Ph3SiCl, which suggests that the silyl chlorides activate CO2 in cooperation with AlBr3. 1H NMR analysis of unworked-up reaction mixtures reveals that the products merge as aluminum carboxylates. The mass balance concerning silicon indicates that the silyl chlorides are recycled during the reaction sequence. On the basis of these observations, a feasible mechanism is proposed for the present carboxylation.
- Nemoto, Koji,Yoshida, Hiroki,Egusa, Naoki,Morohashi, Naoya,Hattori, Tetsutaro
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experimental part
p. 7855 - 7862
(2011/02/21)
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- Optimization of isochromanone based urotensin II receptor agonists
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A series of novel isochromanone based urotensin II receptor agonists have been synthesized and evaluated for their activity using a functional cell based assay (R-SAT). Several potent and efficacious derivatives were identified with 3-(3,4-dichlorophenyl)-6,7-dimethyl-3-(2-dimethylaminoethyl)isochroman-1-one (28) being the most potent compound showing an EC50-value of 51 nM, thereby being the most potent compound so far within the isochromanone series. In addition, two other heterocyclic systems (isochromanes and tetrahydroisoquinolinones) were investigated and these derivatives were found to be both potent and efficacious. The activity of the isochromane derivatives implies that the carbonyl group of the isochromanone is not necessary for activity. Furthermore it was found that the geometry of the heterocycles was more important for receptor interaction than the composition of the heteroatoms present.
- Lehmann, Fredrik,Currier, Erika A.,Olsson, Roger,Ma, Jian-Nong,Burstein, Ethan S.,Hacksell, Uli,Luthman, Kristina
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experimental part
p. 4844 - 4854
(2010/08/06)
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- Structure-based design and synthesis of substituted 2-butanols as nonpeptidic inhibitors of HIV protease: Secondary amide series
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The design, synthesis, and crystallographic analysis of protein- inhibitor complexes is described for a novel series of nonpeptidic HIV protease (HIV Pr) inhibitors. Beginning with a cocrystal structure of a Phe- Pro peptidomimetic bound to the HIV Pr, design was initiated that resulted in the substituted 2-butanol compound 8 as the lead compound (K(i) = 24.5 μM, racemic mixture). Modifications on the initial compound were then made on the basis of its cocrystal structure with HIV Pr and inhibition data, resulting in compounds with enhanced potency against the enzyme (compound 18, K(i) = 0.48 μM). These inhibitors were found to bind to the enzyme essentially as predicted on the basis of the original design hypothesis. Stereospecific synthesis of individual enantiomers confirmed the prediction of a binding preference for the S alcohol stereochemistry. Modest antiviral activity was demonstrated for several of the more potent HIV Pr inhibitors in a HIV-1 infected CEM-SS cell line.
- Reich, Siegfried H.,Melnick, Michael,Pino, Mark J.,Fuhry, Mary Ann M.,Trippe, Anthony J.,Appelt, Krzysztof,Davies II, Jay F.,Wu, Bor-Wen,Musick, Linda
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p. 2781 - 2794
(2007/10/03)
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- Manganese(III)-Mediated Formylation of Aromatic Compounds in the Presence of Malonic Acid
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The reaction of naphthlenes with malonic acid in the presence of manganese(III) acetate gives naphthalenecarbaldehydes and naphthalenecarboxylic acids.Similar reactions of anthracene, pyrene, and methoxybenzenes also yield formylated and carboxylated products.It was found that the formyl group introduced to the aromatic ring was not derived from carboxymethyl radical generated directly by the thermolysis of manganese(III) acetate, but from a dicarboxymethyl radical formed by the interaction of malonic acid and manganese(III) acetate.In addition, it was also found that the dicarboxymethyl radicals attacked the position of the highest electron density on the aromatic ring and that this formylation was effective when the ionization potential of the aromatic copound was lower than 7.8 eV.
- Nishino, Hiroshi,Tsunoda, Katsunori,Kurosawa, Kazu
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p. 545 - 550
(2007/10/02)
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- ELECTRON TRANSFER ACTIVATION. HYDROPEROXIDE INTERMEDIATES IN A NOVEL AND SELECTIVE PROCEDURE FOR BENZYLIC OXIDATIONS.
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A selective and mild photochemical procedure for benzylic oxidations with 9,10-dicyanoanthracene (DCA) an usual electron acceptor, in the presence of methyl viologen (MV2+), an electron relay, has been developed.Methyl and methylene groups are oxidized in good to excellent yields to the corresponding hydroperoxides.
- Santamaria, J.,Jroundi, R.,Rigaudy, J.
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p. 4677 - 4680
(2007/10/02)
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- PHOTOOXYGENATIONS PAR TRANSFERT D'ELECTRON SENSIBILISEES PAR LE DICYANO-9,10 ANTHRACENE. ROLE DU SOLVANT ET FORMATION D'OXYGENE SINGULET.
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Photooxygenation of naphtalenic compounds sensitized by electron acceptors like 9,10 dicyanoanthracene (DCA) is shown to proceed by two distinct ways depending on the solvent polarity.In a polar solvent superoxide ion (O2-.) as well as singlet oxygen (1O2*) are involved while in a non polar solvent only singlet oxygen is produced.
- Santamaria, J.,Gabillet, P.,Bokobza, L.
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p. 2139 - 2142
(2007/10/02)
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