- C-C coupling of ketones with methanol catalyzed by a N-heterocyclic carbene-phosphine iridium complex
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An N-heterocyclic carbene-phosphine iridium complex system was found to be a very efficient catalyst for the methylation of ketone via a hydrogen transfer reaction. Mild conditions together with low catalyst loading (1 mol%) were used for a tandem process which involves the dehydrogenation of methanol, C=C bond formation with a ketone, and hydrogenation of the new generated double bond by iridium hydride to give the alkylated product. Using this iridium catalyst system, a number of branched ketones were synthesized with good to excellent conversions and yields.
- Quan, Xu,Kerdphon, Sutthichat,Andersson, Pher G.
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supporting information
p. 3576 - 3579
(2015/03/04)
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- KINASE INHIBITORS AND METHOD OF TREATING CANCER WITH SAME
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The present teachings provide a compound represented by structural formula (I): or a pharmaceutically acceptable salt thereof. Also described are pharmaceutical compositions and methods of use thereof.
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Paragraph 0241; 0242
(2014/02/15)
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- KINASE INHIBITORS AND METHOD OF TREATING CANCER WITH SAME
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The invention is a compound represented by Structural Formula (I) or a pharmaceutically acceptable salt thereof. Values for the variables are provided herein. Also included is a pharmaceutical composition comprising the compound represented by Structural Formula (I) and a pharmaceutically acceptable carrier or diluent and methods of treating a subject with cancer with the compound of Structural Formula (I).
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Page/Page column 34-35
(2014/05/07)
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- INDAZOLE COMPOUNDS AS KINASE INHIBITORS AND METHOD OF TREATING CANCER WITH SAME
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The present teaching provide indazole compounds represented by Structural Formulae (I) or (I') or a pharmaceutically acceptable salt thereof. Also described are pharmaceutical compositions and methods of use thereof as protein kinase inhibitors, such as T
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Page/Page column 108
(2013/04/25)
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- Intramolecular palladium-catalyzed alkane C-H arylation from aryl chlorides
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The first examples of efficient and general palladium-catalyzed intramolecular C(sp3)-H arylation of (hetero)aryl chlorides, giving rise to a variety of valuable cyclobutarenes, indanes, indolines, dihydrobenzofurans, and indanones, are described. The use of aryl and heteroaryl chlorides significantly improves the scope of C(sp3)-H arylation by facilitating the preparation of reaction substrates. Careful optimization studies have shown that the palladium ligand and the base/solvent combination are crucial to obtaining the desired class of product in high yields. Overall, three sets of reaction conditions employing PtBu3, PCyp3, or PCy3 as the palladium ligand and K 2CO3/DMF or Cs2CO3/pivalic acid/mesitylene as the base/solvent combination allowed five different classes of products to be accessed using this methodology. In total, more than 40 examples of C-H arylation have been performed successfully. When several types of C(sp3)-H bond were present in the substrate, the arylation was found to occur regioselectively at primary C-H bonds vs secondary or tertiary positions. In addition, in the presence of several primary C-H bonds, selectivity trends correlate with the size of the palladacyclic intermediate, with five-membered rings being favored over six- and seven-membered rings. Regio- and diastereoselectivity issues were studied computationally in the prototypal case of indane formation. DFT(B3PW91) calculations demonstrated that C-H activation is the rate-determining step and that the creation of a C-H agostic interaction, increasing the acidity of a geminal C-H bond, is a critical factor for the regiochemistry control.
- Rousseaux, Sophie,Davi, Michael,Sofack-Kreutzer, Julien,Pierre, Cathleen,Kefalidis, Christos E.,Clot, Eric,Fagnou, Keith,Baudoin, Olivier
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supporting information; experimental part
p. 10706 - 10716
(2010/09/17)
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- Insertion of arynes into carbon-halogen σ-bonds: Regioselective acylation of aromatic rings
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Arynes were found to insert into carbon-halogen σ-bonds of various acid halides, enabling acyl and halogen moieties to be introduced simultaneously into adjacent positions of aromatic rings. The Royal Society of Chemistry.
- Yoshida, Hiroto,Mimura, Yasuhiro,Ohshita, Joji,Kunai, Atsutaka
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p. 2405 - 2407
(2008/02/08)
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- Cyclic enolates of Ni and Pd: Equilibrium between C- and O-bound tautomers and reactivity studies
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2-Acylaryl complexes of Ni and Pd containing chelating diphosphines react with KtBuO to give metallacyclic enolate complexes. While coordination through the carbon atom is preferred in the case of Pd, the nickel O-enolate compounds are formed as the corresponding O-tautomers. Slow equilibration between O- and C-enolate tautomers is observed for the nickel complex with an unsubstituted enolate function (M-O-C=CH2). Theoretical DFT calculations suggest that the barrier for the tautomer exchange has its origin in the rigidity of the metallacycle. Whilst the C-enolate tautomer is unreactive towards aldehydes, the corresponding O-enolate adds to MeCHO and PhCHO, giving rise to products that retain the enolate functionality. The carbonylation of these products cleanly leads to the formation of enol lactones in a highly selective manner.
- Campora, Juan,Maya, Celia M.,Palma, Pilar,Carmona, Ernesto,Gutierrez, Enrique,Ruiz, Caridad,Graiff, Claudia,Tiripicchio, Antonio
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p. 6889 - 6904
(2007/10/03)
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- Mechanisms of Elimination Reactions. 39. Steric and Electronic Effects on Stereochemistry in Eliminations from Primary Alkyltrimethylammonium Salts
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Percentages of syn elimination have been determined by high-field NMR on the products of elimination from R1R2CHCHDX.The results for X=OTs with t-BuO(-)/t-BuOH at 60 deg C were the following (R1, R2, percent syn): p-MeOC6H4, C6H5, 3.7; p-ClC6H4, C6H5, 29; p-ClC6H4, C6H5, 0 in EtO(-)/EtOH.For X=NMe3(+) with OH(-) in 50 molpercent Me2SO-50 molpercentH2O at 60 deg C, the results were as follows (R1, R2, percent syn): p-MeOC6H4, C6H5, 60; p-ClC6H4, C6H5, 72.For Ar(i-Pr)CHCHDNMe3(+) with OH(-) in 50 molpercent Me2SO-50 molpercent H2O at 80 deg C, the results were as follows (Ar, percent syn): m-ClC6H4, 78.6; p-ClC6H4, 69.5; C6H5, 59.6; p-EtC6H4, 58.3; p-t-BuC6H4, 60.5.Overall rates in this series were dissected into syn and anti rates, which fitted the Hammett equation to give ρsyn=3.69 +/- 0.20 and ρanti=3.02 +/- 0.22.This result supports the conclusion that syn elimination has a more carbanionic transition state than anti.The lower percent syn with X=OTs than with X=NMe3(+) is ascribed to the lesser steric requirements of OTs.
- Dohner, Brent R.,Saunders, William H. Jr.
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p. 245 - 247
(2007/10/02)
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