- Reductive cyanation of organic chlorides using CO2 and NH3 via Triphos–Ni(I) species
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Cyano-containing compounds constitute important pharmaceuticals, agrochemicals and organic materials. Traditional cyanation methods often rely on the use of toxic metal cyanides which have serious disposal, storage and transportation issues. Therefore, there is an increasing need to develop general and efficient catalytic methods for cyanide-free production of nitriles. Here we report the reductive cyanation of organic chlorides using CO2/NH3 as the electrophilic CN source. The use of tridentate phosphine ligand Triphos allows for the nickel-catalyzed cyanation of a broad array of aryl and aliphatic chlorides to produce the desired nitrile products in good yields, and with excellent functional group tolerance. Cheap and bench-stable urea was also shown as suitable CN source, suggesting promising application potential. Mechanistic studies imply that Triphos-Ni(I) species are responsible for the reductive C-C coupling approach involving isocyanate intermediates. This method expands the application potential of reductive cyanation in the synthesis of functionalized nitrile compounds under cyanide-free conditions, which is valuable for safe synthesis of (isotope-labeled) drugs.
- Dong, Yanan,Li, Yuehui,Yang, Peiju,Zhao, Shizhen
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- Homoleptic ruthenium(iii) chalcogenolates: A single precursor to metal chalcogenide nanoparticles catalyst
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Eight homoleptic metal(iii) arylchalcogenolate polymers [M(EPh-p-X) 3]n (M = Ru, Cr, and Mo) were characterized by PXRD. Structural solution of [Ru(SPh-p-tBu)3]n1 was achieved by Rietveld refinement of the PXRD data. Pyrolysis of [Ru(SePh)3] n4 produced nanostructured RuSe2, which selectively catalyzed the reduction of nitro compounds in the presence of other functionalities.
- Chan, Sharon Lai-Fung,Low, Kam-Hung,So, Gary Kwok-Ming,Chui, Stephen Sin-Yin,Che, Chi-Ming
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supporting information; experimental part
p. 8808 - 8810
(2011/10/02)
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- SULFONYL AMIDE DERIVATIVES FOR THE TREATMENT OF ABNORMAL CELL GROWTH
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The present invention relates to a compound of the formula I wherein R1 to R6, A, B, n and m are as defined herein. Such novel sulfonyl amide derivatives are useful in the treatment of abnormal cell growth, such as cancer, in mammals. This invention also relates to a method of using such compounds in the treatment of abnormal cell growth in mammals, especially humans, and to pharmaceutical compositions containing such compounds.
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Page/Page column 39
(2009/04/24)
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- Ferrous sulfide/aqueous ammonia: Simple, efficient, and chemoselective reagent for the conversion of aromatic azide to amine
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A practical, environmentally benign, rapid, and efficient method for the reduction of aromatic azide to amine is described using FeS/aqueous ammonia in the presence of other reducible functionalities. Application of a novel reducing reagent results in aromatic amines with excellent yield and high chemoselectivity, without need of any purification techniques. Copyright Taylor & Francis Group, LLC.
- Gadakh, Amol V.,Karale, Bhausaheb K.
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p. 186 - 191
(2008/03/17)
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- AMIDINOHYDRAZONES AS PROTEASE INHIBITORS
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Amidino and benzamidino compounds, including compounds of the formula: I wherein R1-R4, R6-R9, Y, Z, n and m are set forth in the specification, as well as hydrates, solvates or pharmaceutically acceptable salts thereof, that inhibit proteolytic enzymes such as thrombin are described. Also described are methods for preparing the compounds of Formula I.
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Page/Page column 46
(2010/11/23)
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- Sandmeyer reactions. Part 5.1 Estimation of the rates of 1,5-aryl/aryl radical translocation and cyclisation during Pschorr fluorenone synthesis with a comparative analysis of reaction energetics
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During the Pschorr cyclisation of 2-aroylphenyl radicals, a rearrangement occurs reversibly by 1,5-hydrogen transfer to give 2-benzoylaryl radicals. Rate constants of (1.2 ± 0.2) × 106 s-1 at 293 K are estimated for both the forward and back reactions in the equilibrium between 2-(4-methylbenzoyl)phenyl and 2-benzoyl-5-methylphenyl radicals. Assuming an empirical estimate of 1.6 × 10-2 dm3 mol-1 s-1 for the hypothetical rate of abstraction of hydrogen from benzene by phenyl radicals, the radical translocation is calculated to occur with a statistically corrected effective molarity of 2.2 × 108 mol dm-3. By contrast, the competing cyclisation, though occurring at a rate of (8.0 ± 0.9) × 105 s-1, exhibits an effective molarity of only 5.3 mol dm-3. The causes of these differences are analysed in terms of reaction mechanism.
- Chandler, Stephen A.
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p. 214 - 228
(2007/10/03)
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- AMIDINOHYDRAZONES AS PROTEASE INHIBITORS
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Amidino and benzamidino compounds, including compounds of the formula: STR1 wherein R 1-R 4, R 6-R 9, Y, Z, n and m are set forth in the specification, as well as hydrates, solvates or pharmaceutically acceptable salts thereof, that inhibit proteolytic enzymes such as thrombin are described. Also described are methods for preparing the compounds of Formula I.
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