20409-48-7Relevant academic research and scientific papers
Synthesis, Solid-state and Solution Structures of Bis(N,N'-bis-1,2-diaminoethane)-silver(I) and -copper(I) Trifluoromethanesulfonate Complexes
Modder, Johan F.,Leijen, Ronald J.,Vrieze, Kees,Smeets, Wilberth J. J.,Spek, Anthony L.,Koten, Gerard van
, p. 4021 - 4028 (1995)
Reaction of 2 equivalents of the thienyl ketimines 2C2H4 (R = Me or SC4H3) with 1 equivalent of M'(O3SCF3) (M = Ag or Cu) resulted in formation of stable 2C2H4)2> complexes.The crystal structures of 2C2H4)2> and 2C2H4)2> have been determined.Both unit cells contain discrete anions and, basically isostructural, complex cations.The co-ordination sphere of the metal(I) centre is dominated by four imine N atoms provided by two symmetrically, bidentate co-ordinating 2C2H4 ligands.Four thiophene S atoms are also in proximity of the metal nucleus , but do not co-ordinate.The AgN4 geometry is flattened, as indicated by the spatial geometry of the four donor atoms, and tends more to square planar than to the usual tetrahedral arrangement.The CuN4 geometry is slightly compressed from tetrahedral.A characteristic of these complexes is their very low solubility which makes further spectroscopic studies difficult.Various 1H NMR experiments have established that the complex cations are isostructural, having a tetrahedral co-ordination geometry similar to that found in the crystals, comprising symmetrically co-ordinating, bidentate ligands.There are no indications that the solution structure is compressed.The solution structure is only kinetically stable at low temperatures (/= 180 K); at more elevated temperatures ligand exchange occurs, which is rapid at ambient temperatures.
N-Heterocyclic Carbene-Catalyzed Decarboxylative Alkylation of Aldehydes
Ishii, Takuya,Kakeno, Yuki,Nagao, Kazunori,Ohmiya, Hirohisa
supporting information, p. 3854 - 3858 (2019/04/25)
We found that N-heterocyclic carbene catalysis promoted the unprecedented decarboxylative coupling of aryl aldehydes and tertiary or secondary alkyl carboxylic acid-derived redox-active esters to produce aryl alkyl ketones. The mild and transition-metal-free reaction conditions are attractive features of this method. The power of this protocol was demonstrated by the functionalization of pharmaceutical drugs and natural product. A reaction pathway involving single electron transfer from an enolate form of Breslow intermediate to a redox ester followed by recombination of the resultant radical pair to form a carbon-carbon bond is proposed.
Cp?Co(III)-Catalyzed C-H Alkylation with Maleimides Using Weakly Coordinating Carbonyl Directing Groups
Mandal, Rajib,Emayavaramban, Balakumar,Sundararaju, Basker
supporting information, p. 2835 - 2838 (2018/05/29)
A novel protocol for ortho-C-H alkylation of aromatic and heteroaromatic ketones and esters under Cp?Co(III) catalysis has been developed for the first time. The reaction proceeds through initial cyclometalation via weak chelation-assisted C-H bond activation, followed by coordination of activated alkene, insertion between Co-C, and protodemetalation.
Transition metal complex, the dye and pigment-containing oxide semiconductor electrode and dye-sensitized solar cell
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Paragraph 0124-0126, (2016/12/12)
PROBLEM TO BE SOLVED: To provide a transition metal complex which exhibits strong absorptions in a wide range of spectra and serves as a novel photosensitizer dye having excellent durability, as well as an oxide semiconductor electrode and a dye-sensitized solar cell that contain the dye. SOLUTION: The bivalent transition metal including (i) a bipyridyl polyacidic ligand such as a dicarboxybipyridyl (dcbpy) ligand as an adsorption site for adsorption onto the surface of titanium dioxide particles, (ii) a ligand which is selected from among isothiocyanato, isocyanato, and isoselenato groups and enables absorption excitation/charge transfer at long wavelengths, and (iii) a bipyridyl (bpy) ligand directly bonded to or conjugated to a five-membered heterocyclic ring having an alkyl, an alkoxyalkyl, or an alkoxy group including a quaternary carbon atom which may be optionally substituted by one or more fluoro groups for providing nucleophilic reagent stability to a sensitizer dye to improve the absorbance and bathochromic effect in absorption of the transition metal complex, and the photosensitizer dye having the structure are provided. COPYRIGHT: (C)2011,JPOandINPIT
Preparation of acylthiophenes by iron(III) chloride catalyzed reactions of tris(2-thienyl)stibanes with acyl chlorides
Kakusawa, Naoki,Nakagawa, Yoshie,Toshima, Yutarou,Yasuike, Shuji,Kurita, Jyoji
, p. 1170 - 1175 (2015/07/15)
The reactions of tris(2-thienyl)stibanes with various acyl chlorides, using a catalytic amount of iron(III) chloride, afforded 2-acylthiophenes. Iron(III) chloride is presumed to act as a Lewis acid, and the ipso substituent of each 2-thienyl group of tris(2-thienyl)stibane is replaced with an acyl group. The reaction is highly atom-efficient in that all three thiophene rings of tris(2-thienyl)stibane take part in the reaction. The reaction procedure is so simple that it can also be carried out under solvent-free and aerobic conditions.
Efficient aerobic oxidation of secondary alcohols at ambient temperature with an ABNO/NOx catalyst system
Lauber, Markus B.,Stahl, Shannon S.
, p. 2612 - 2616 (2013/11/19)
New highly practical methods are presented for aerobic oxidation of secondary alcohols with a nitroxyl radical in combination with HNO3, NaNO2, or both as cocatalysts. Diverse nitroxyls are compared, including several novel bicyclic derivatives. Catalyst systems with the readily available nitroxyls, 9-azabicyclo[3.3.1]nonane-N-oxyl (ABNO) and 9-azabicyclo[3.3.1]nonan-3-one-N-oxyl (keto-ABNO), are optimized in acetic acid or acetonitrile as the solvent. The reactions are compatible with substrates bearing diverse functional groups and proceed efficiently under mild conditions at ambient pressure and temperature.
On the NH effect in ruthenium-catalysed hydrogenation of ketones: Rational design of phosphine-amino-alcohol ligands for asymmetric hydrogenation of ketones
Phillips, Scott D.,Fuentes, Jose A.,Clarke, Matthew L.
supporting information; experimental part, p. 8002 - 8005 (2010/09/14)
Chemical equation presented Redesign and reduce: The graphic shows some Ru complexes of tridentate ligands that do not contain NH substituents but can catalyse ketone reduction with zero-order dependence on ketone. In tridentate systems, a secondary amine, not a primary amine, promotes hydrogen activation. Leading on from these observations, the Ru complex of a phosphine-amino-alcohol shown above has been found to be a good hydrogenation catalyst.
RUTHENIUM COMPLEX AND PROCESS FOR PRODUCING TERT-ALKYL ALCOHOL THEREWITH
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Page/Page column 8, (2010/11/28)
A tert-alkyl ketone, pinacolone was hydrogenated under pressurized hydrogen in the presence of a ruthenium complex (S)-1 and a base, and corresponding (S)-3,3,-dimethyl-2-butanol was thereby obtained in 100% yield and 97% ee.
Asymmetric hydrogenation of tert-alkyl ketones
Ohkuma, Takeshi,Sandoval, Christian A.,Srinivasan, Rajagopal,Lin, Quinghong,Wei, Yinmao,Muniz, Kilian,Noyori, Ryoji
, p. 8288 - 8289 (2007/10/03)
A combined system of RuCl2(tolbinap)(pica) and an alkaline or organic phosphazene base catalyzes asymmetric hydrogenation of sterically congested tert-alkyl ketones (TolBINAP = 2,2-bis(di-4-tolylphosphino)-1,1-binaphthyl, PICA = α-picolylamine). Hydrogenation with RuH(η1-BH4)(tolbinap)(pica) does not require any strong base. Alcoholic solvents strongly affect the catalytic efficiency. The reaction proceeds smoothly in ethanol under 1-20 atm of H2 and at room temperature with a substrate to catalyst molar ratio of up to 100000. Various aliphatic, aromatic, heteroaromatic, and olefinic tert-alkyl ketones are convertible to the corresponding chiral carbinols in high enantiomeric purity. Olefinic and heteroaromatic functions are left intact. Certain cyclic ketones are also usable. The mode of enantioface selection is consistent and predictable. Copyright
Zinc promoted regioselective friedel-crafts acylation of electron rich arenes
Meshram,Reddy, Gondi Sudershan,Muralidhar Reddy,Yadav
, p. 2203 - 2206 (2007/10/03)
A simple and convenoent zinc promoted selective Friedel-Crafts acylation is described. The inexpensive metal grade catalyst and minimum waste effluent are the important features of the procedure.
