- Long-Range Self-Assembly of an Electron-Deficient Hexaazatrinaphthylene with Out-of-Plane Substituents
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The unprecedented time-dependent long-range supramol-ecular assembly of electron-deficient hexaazatrinaphthylene (HATN) core based on peripheral crowding with three out-of-plane cyclic ketals is reported. The single-crystal X-ray structure of the diethyl derivative provided detailed information as to how four molecules in a repeating unit were packed in order to avoid steric crowding of the out-of-plane cyclic ketal side chain, providing locking and fastening for stabilizing the self-assembled structure. The polarizing optical microscopy (POM) and differential scanning calorimetry (DSC) did not instantaneously show any phase transition upon the cooling process. To our surprise, POM images showed a nucleation of spherulite up to 100 μm after 24 hour later. X-ray diffraction data further confirmed that these soft crystal formed a hexagonal-like crystal. The long-range self-assembly of the new material showed a slight red shift in the UV-vis absorption spectra and further substantiated by computational method.
- Chen, Yi-Ru,Zhang, Yong-Yun,Yeh, Ming-Che,Luo, Ying-Ting,Ong, Chi Wi
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p. 613 - 618
(2019/12/24)
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- Deoxygenation of heptanoic acid to hexene over cobalt-based catalysts: A model study for α-olefin production from renewable fatty acid
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Deoxygenation of heptanoic acid, a model compound, over bimetallic cobalt (Co-Pt, Co-Au, Co-Pd, Co-Ru) supported silica catalysts, was examined for α-olefin production. The catalysts were prepared by conventional impregnation of the metal precursors on silica and characterized by XRF, TEM, H2-TPR, acetic acid-TPD, and XANES. Catalytic testing was performed in a fixed-bed flow reactor under atmospheric H2 pressure. Monometallic cobalt catalysts yielded mainly 1-hexene, but rapid deactivation was observed. Incorporation of 0.5percentwt secondary metal, particularly Pt, increases activity and stability under H2. A relatively higher olefin/paraffin ratio can be obtained from the reaction over 5percentCo+0.5percentPt/SiO2 when compared to that with higher Pt loading. The co-impregnation method offers Co-Pt catalysts with stability higher than that prepared by the sequential impregnation method. Over cobalt-based catalysts, the deoxygenation is proposed to proceed via reduction of heptanoic acid to heptanal that is an intermediate for decarbonylation to hexene; while other side reactions are suppressed.
- Choojun, Kittisak,Phichitsurathaworn, Ploynisa,Poo-arporn, Yingyot,Sooknoi, Tawan
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- Highly productive α-alkylation of ketones with alcohols mediated by an Ir-oxalamidato/solid base catalyst system
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An Ir-oxalamidato complex in combination with a solid base (e.g., magnesium aluminometasilicate/Ca(OH)2) significantly improved the catalyst productivity in α-alkylation of methyl ketones with primary alcohols. Optimization through systematic variation of the oxalamidato ligand led to a practical turnover number (TON) of 10 000.40 000.
- Maeda, Hironori,Nara, Hideki,Shimizu, Hideo
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supporting information
p. 2772 - 2779
(2020/12/29)
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- Dehydrogenative Coupling of Benzylic and Aldehydic C-H Bonds
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A photoinduced dehydrogenative coupling reaction between benzylic and aldehydic C-H bonds is reported. When a solution of an alkylbenzene and an aldehyde in ethyl acetate is irradiated with visible light in the presence of iridium and nickel catalysts, a coupled α-aryl ketone is formed with evolution of dihydrogen. An analogous C-C bond forming reaction occurs between a C-H bond next to the nitrogen of an N-methylamide and an aldehydic C-H bond to produce an α-amino ketone. These reactions provide a straightforward pathway from readily available materials leading to valued structural motifs of pharmacological relevance.
- Ishida, Naoki,Kawasaki, Tairin,Murakami, Masahiro
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supporting information
p. 3366 - 3370
(2020/03/06)
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- IONIZABLE CATIONIC LIPID FOR RNA DELIVERY
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What is described is a compound of formula I consisting of a compound in which R1 is a branched chain alkyl consisting of 10 to 31 carbons; R2 is a linear alkyl, alkenyl, or alkynyl consisting of 2 to 20 carbons; L1 and L2 are the same or different, each a linear alkylene of 1 to 20 carbons or a linear alkenylene of 2 to 20 carbons; X1 is S or O; R3 is a linear or branched alkylene consisting of 1 to 6 carbons; and R4 and R5 are the same or different, each a hydrogen or a linear or branched alkyl consisting of 1 to 6 carbons; or a pharmaceutically acceptable salt thereof.
- -
-
-
- IONIZABLE CATIONIC LIPID FOR RNA DELIVERY
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What is described is a compound of formula I consisting of a compound in which R1 is a branched chain alkyl consisting of 10 to 31 carbons;R2 is a linear alkyl, alkenyl, or alkynyl consisting of 2 to 20 carbons, or a branched chain alkyl consisting of 10 to 31 carbons;L1 and L2 are the same or different, each a linear alkane of 1 to 20 carbons or a linear alkene of 2 to 20 carbons;X1 is S or O;R3 is a linear or branched alkylene consisting of 1 to 6 carbons; andR4 and R5 are the same or different, each a hydrogen or a linear or branched alkyl consisting of 1 to 6 carbons; or a pharmaceutically acceptable salt thereof.
- -
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- Chelation-Assisted C-H and C-C Bond Activation of Allylic Alcohols by a Rh(I) Catalyst under Microwave Irradiation
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Chelation-assisted Rh(I)-catalyzed ketone synthesis from allylic alcohols and alkenes through C-H and C-C bond activations under microwave irradiation was developed. Aldimine is formed via olefin isomerization of allyl alcohol under Rh(I) catalysis and condensation with 2-amino-3-picoline, followed by continuous C-H and C-C bond activations to produce a dialkyl ketone. The addition of piperidine accelerates the reaction rate by promoting aldimine formation under microwave conditions.
- Lee, Chang-Hee,Jun, Chul-Ho
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p. 736 - 741
(2017/11/27)
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- Cerium oxide as a catalyst for the ketonization of aldehydes: Mechanistic insights and a convenient way to alkanes without the consumption of external hydrogen
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The ketonization of aldehydes joins two molecules, with n carbon atoms each, to a ketone with 2n - 1 carbon atoms. When employing cerium oxide as a catalyst with nano-sized crystals (15 nm) the ketone can be obtained in almost 80% yield. In addition, other ketones are observed so that the total ketone selectivity reached almost 90%. Water is consumed during the reaction when the aldehyde is oxidized to the corresponding carboxylic acid, which is established as a reaction intermediate, co-producing hydrogen. Consequently, water has to be co-fed in the reaction to enhance the reaction rate and to improve the catalyst stability with time on stream. In contrast to zirconium oxide which possesses catalytic activity for the aldol condensation liberating water, with cerium oxide water is not abundant on the surface and the reaction kinetics show that the reaction rate depends on the concentration of the water in the gas-phase, in addition to the dependence on the gas-phase concentration of the aldehyde. The liberated hydrogen can be consumed in the hydrodeoxygenation of the ketone product. Doing so, when starting from heptanal, a biomass derived aldehyde, an alkane mixture was obtained with almost 90% diesel content. For the whole cascade reaction with five single steps no reagents are necessary and the only by-product is one molecule of innocuous carbon dioxide (related to two molecules of aldehyde). This shows that cerium oxide possesses a big potential to convert biomass derived aldehydes into biofuels in a very sustainable way.
- Orozco, Lina M.,Renz, Michael,Corma, Avelino
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supporting information
p. 1555 - 1569
(2017/05/10)
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- Carbon–Carbon Bond Formation and Hydrogen Production in the Ketonization of Aldehydes
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Aldehydes possess relatively high chemical energy, which is the driving force for disproportionation reactions such as Cannizzaro and Tishchenko reactions. Generally, this energy is wasted if aldehydes are transformed into carboxylic acids with a sacrificial oxidant. Here, we describe a cascade reaction in which the surplus energy of the transformation is liberated as molecular hydrogen for the oxidation of heptanal to heptanoic acid by water, and the carboxylic acid is transformed into potentially industrially relevant symmetrical ketones by ketonic decarboxylation. The cascade reaction is catalyzed by monoclinic zirconium oxide (m-ZrO2). The reaction mechanism has been studied through cross-coupling experiments between different aldehydes and acids, and the final symmetrical ketones are formed by a reaction pathway that involves the previously formed carboxylic acids. Isotopic studies indicate that the carboxylic acid can be formed by a hydride shift from the adsorbed aldehyde on the metal oxide surface in the absence of noble metals.
- Orozco, Lina M.,Renz, Michael,Corma, Avelino
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p. 2430 - 2442
(2016/10/24)
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- Decarbonylation of heptanoic acid over carbon-supported platinum nanoparticles
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The decarbonylation and decarboxylation of heptanoic acid over carbon-supported Pt nanoparticles were studied in a continuous flow fixed bed reactor at 573 K and 37 bar for liquid-phase operation and 1 bar for gas-phase operation. Under liquid-phase conditions, the TOF over Pt supported on Norit carbon was 0.0052 s-1 and independent of Pt loading. At very low conversions, approaching zero, the product selectivity was consistent with decarbonylation as the primary reaction, producing mostly hexenes and CO. As conversion increased from 1% to 5% at 37 bar, substantial amounts of hexane and CO2 were observed, presumably from secondary side reactions such as water-gas shift (WGS) and hydrogenation instead of direct decarboxylation. The terminal olefin was observed with high selectivity (57%) only during gas-phase operation (1 bar) which facilitated transport of the olefin away from the Pt that also catalyzed double bond isomerization. Some sintering of the Pt metal particles during reaction of heptanoic acid was observed by X-ray diffraction analysis of the spent catalyst. Catalyst regeneration studies were performed over spent catalyst but they failed to restore any catalytic activity.
- Lopez-Ruiz, Juan A.,Davis, Robert J.
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p. 683 - 694
(2014/02/14)
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- Synthesis of symmetrical ketones from Grignard reagents and 1,1′-carbonyldiimidazole
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Coupling reactions of 1,1′-carbonyldiimidazole with Grignard reagents provide a rapid and straightforward method for the synthesis of symmetrical ketones. Georg Thieme Verlag Stuttgart.
- Bottalico, Daniela,Fiandanese, Vito,Marchese, Giuseppe,Punzi, Angela
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experimental part
p. 2316 - 2318
(2010/02/28)
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- Rhodium(I)-catalyzed one-pot synthesis of dialkyl ketones from methanol and alkenes through directed sp3 C-H bond activation of N-methylamine
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The hydroacylation of methanol with alkenes was developed using a catalytic system consisting of Rh(i), 2-amino-4-picoline and benzoic acid; the reaction is speculated to occur by the initial N-methylation of 2-amino-4-picoline with methanol, and the subsequent dehydrogenation of the resulting N-methylamine, followed by double chelation-assisted hydroimination of alkene with the imine to give dialkyl ketones after hydrolysis. The Royal Society of Chemistry.
- Jo, Eun-Ae,Lee, Ji-Hyun,Jun, Chul-Ho
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body text
p. 5779 - 5781
(2009/04/13)
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- Oxalic acid catalyzed reaction between dithioacetals and acetals. A simple and eco-friendly method for a conversion of a dithioacetal to a carbonyl compound
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Oxalic acid catalyzes a reaction between dithioacetals and acetals. This reaction is useful in a new and eco-friendly method to convert dithioacetals to carbonyl compounds.
- Miyake, Hideyoshi,Nakao, Yuichi,Sasaki, Mitsuru
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p. 6247 - 6250
(2007/10/03)
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- Pentamethylcyclopentadienide in organic synthesis: Nucleophilic addition of lithium pentamethylcyclopentadienide to carbonyl compounds and carbon-carbon bond cleavage of the adducts yielding the parent carbonyl compounds
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Lithium pentamethylcyclopentadienide (C5Me5Li, Cp*Li) reacted with aromatic aldehyde to provide the corresponding carbinol in excellent yield. The carbinol returns to the parent aldehyde and pentamethylcyclopentadiene upon exposure to acid or due to heating. Chlorodimethylaluminum is essential as an additive to attain the nucleophilic addition of Cp*Li to aliphatic aldehyde. The carbinol derived from aliphatic aldehyde returns to the parent aldehyde and pentamethylcyclopentadiene by the action of a catalytic amount of 2,3-dichloro-5,6-dicyanobenzoquinone (DDQ). The reversible addition/elimination of the Cp* group can represent a protection of aldehyde. Mechanistic details of the carbon-carbon bond cleavage are also disclosed.
- Uemura, Minoru,Yagi, Kazunari,Iwasaki, Masayuki,Nomura, Kenichi,Yorimitsu, Hideki,Oshima, Koichiro
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p. 3523 - 3535
(2007/10/03)
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- Catalytic ketonisation over oxide catalysts. Part IX. Single step synthesis of aliphatic saturated and unsaturated C11 - C 13 ketones from carboxylic acids
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Metameric undecan-x-ones (x = 2-6), dodecan-y-ones (y = 2-5), tridecan-z-ones (z = 4-7) and two unsaturated aliphatic ketones were prepared by vapor phase ketonisation of the appropriate monocarboxylic acids in the presence of 20 wt% MnO2/Al2O3 catalyst under flow conditions. The ketones were obtained in yields between 48 and 89% in a multigram scale (80-250 g). Their physical and spectral data have been determined.
- Glinski,Gibka
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p. 299 - 302
(2007/10/03)
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- Catalytic ketonisation over oxide catalysts. Part VII. Ketonisation and cross-ketonisation of aliphatic esters over CeO2 and ZrO2 supported on alumina
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Catalysts of general formula xwt% MO2/Al2O 3, where x = 10, 20 or 30 and M = Ce or Zr have been studied in the ketonisation and cross-ketonisation of aliphatic esters under flow conditions between 548-723 K. Ketonisation of ethyl pentanoate, heptanoate and nonanoate has led to nonan-5-one, tridecan-7-one and heptadecan-9-one, respectively. The conversion of esters increased with temperature and at 698 K a quantitative conversion was observed, irrespective of the type of ester used. A maximum yield of ketone (46% for nonan-5-one, 60% for tridecan-7-one and 50% for heptadecan-9-one) was observed at 673 K. As a result of the cross-ketonisation of a mixture of ethyl pentanoate and ethyl nonanoate (3:1 molar ratio), three ketones were formed: nonan-5-one, tridecan-5-one and heptadecan-9-one. At 698 K, maximum yields of ketones were noted (37, 46 and 8%, respectively) together with a 90% conversion of esters. The catalysts were characterized by XRD, TPR and surface area measurements.
- Glinski,Szymanski,Lomot
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p. 1033 - 1038
(2007/10/03)
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- N-tert-Butylbenzenesulfenamide-catalyzed oxidation of alcohols to the corresponding carbonyl compounds with N-chlorosuccinimide
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N-tert-Butylbenzenesulfenamide (1)-catalyzed oxidation of various primary and secondary alcohols to the corresponding aldehydes and ketones was efficiently carried out by using N-chlorosuccinimide (NCS) in the coexistence of potassium carbonate and molecular sieves 4? at easy-to-control temperatures ranging from 0°C to room temperature. The present catalytic oxidation was performed without giving any damage to the functional groups in alcohols, and was particularly effective in the oxidation of alcohols that formed labile aldehydes because of its mild reaction conditions. Further, selective oxidation of primary hydroxy groups took place in 1-catalyzed oxidation of several diols. Mechanistic investigation suggested that the chlorination of the sulfenamide 1 by NCS led to the formation of a key species, N-tert-butylbenzenesulfinimidoyl chloride (2), which in turn oxidized alcohols in the presence of potassium carbonate to afford carbonyl products by accompanying regeneration of the catalyst 1.
- Matsuo, Jun-Ichi,Iida, Daisuke,Yamanaka, Hiroyuki,Mukaiyama, Teruaki
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p. 6739 - 6750
(2007/10/03)
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- Sulfenamide-catalyzed oxidation of primary and secondary alcohols with molecular bromine
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Primary and secondary alcohols were smoothly oxidized to the corresponding aldehydes and ketones in high yields at room temperature with 1.1 equiv. of molecular bromine by using a catalytic amount of N-t-butyl-2-nitrobenzenesulfenamide in the coexistence of potassium carbonate and molecular sieves 4A.
- Matsuo, Jun-Ichi,Kawana, Asahi,Yamanaka, Hiroyuki,Mukaiyama, Teruaki
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p. 182 - 183
(2007/10/03)
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- Synthesis of cycloalkanones from dienes and allylamines through C-H and C-C bond activation catalyzed by a rhodium(I) complex
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Formaldehyde in disguise: The allylic amine 1 is used as a masked form of formaldehyde in the rhodium-catalyzed cyclization of dienes 2. The reaction provides access to various cycloalkanones 3 through chelation-assisted C-H- and C-C-bond activation.
- Lee, Dae-Yon,Kim, In-Jung,Jun, Chul-Ho
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p. 3031 - 3033
(2007/10/03)
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- Application of Rh(l)-Catalyzed C - H Bond Activation to the Ring Opening of 2-Cycloalkenones in the Presence of Amines
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(matrix presented) Herein described is the application of the Rh(l)-catalyzed C-H bond activation to the ring-opening of 2-cycloalkenones in the presence of cyclohexylamine. This reaction includes the C-C double bond cleavage of 2-cycloalkenones through the conjugate addition of cyclohexylamine followed by the retro-Mannich-type fragmentation. The resulting ring-opened intermediates subsequently underwent either chelation-assisted hydroacylation to afford a ring-opened dicarbonyl compound or β-alkylation via a ring contraction.
- Jun, Chul-Ho,Moon, Choong Woon,Lim, Sung-Gon,Lee, Hyuk
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p. 1595 - 1597
(2007/10/03)
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- Barbier-type addition of alkyl halides to aldehydes promoted by pentacarbonyliron
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The yield and structure of products of the Barbier-type addition of alkyl halides (perfluorobutyl iodide, allyl bromide, allyl iodide, and hexyl iodide) to para-substituted benzaldehydes in the presence of pentacarbonyliron are essentially determined, on the one hand, by the ability of alkyl halide to be reduced to carbanion and, on the other, by the electrophilicity of the aldehyde reaction center which in turn depends on the nature of para-substituent in the aromatic ring.
- Vasil'Eva,Mysova,Chakhovskaya,Terent'Ev
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p. 1014 - 1017
(2007/10/03)
-
- Synthesis and antimalarial activity of novel medium-sized 1,2,4,5-tetraoxacycloalkanes
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CsOH- or Ag2O-mediated cycloalkylation of (alkylidene)bisperoxides 3 and 1,n-dihaloalkanes (n = 3-8) provided the corresponding medium-sized 1,2,4,5-tetraoxacycloalkanes 4-8 in moderate yields. Subsequent evaluation of the antimalarial activity of the cyclic peroxides 4-8 in vitro and in vivo revealed that 1,2,6,7-tetraoxaspiro[7.11]nonadecane 4a has considerable potential as a new, inexpensive, and potent antimalarial drug.
- Kim,Nagai,Ono,Begum,Wataya,Hamada,Tsuchiya,Masuyama,Nojima,McCullough
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p. 2357 - 2361
(2007/10/03)
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- Catalytic activation of C-H and C-C bonds of allylamines via olefin isomerization by transition metal complexes
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(matrix presented) The metal-catalyzed reaction of olefins with allylamines bearing coordination sites (2-pyridyl groups) was studied. With Ru3(CO)12 as catalyst, activation of C-H bonds led to the formation of ketimines that were hydrolyzed to give asymmetric ketones. With [(C8H14)2RhCl]2, both C-H and C-C bonds were activated and symmetric ketones were formed on hydrolysis. The reaction involves double bond migration of the allylamine to form an aldimine.
- Jun, Chul-Ho,Lee, Hyuk,Park, Jae-Bum,Lee, Dae-Yon
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p. 2161 - 2164
(2008/02/11)
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- S,S-dimethyl dithiocarbonate: A novel carbonyl dication synthon in the synthesis of ketones
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We report herein the use of DMDTC as an effective carbonyl dication equivalent in ketone synthesis. According to our strategy, we also successfully devised a synthetic pathway for S-methyl (trimethylsilyl)thioacetate which may be a potentially useful synthetic reagent in organic synthesis.
- Chen, Chiar-Dy,Huang, Jui-Wen,Leung, Man-Kit,Li, Huei-Hsu
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p. 9067 - 9078
(2007/10/03)
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- The CoCl2/Ph(Et)2N:BH3/CO system: Reactions of the borane and cobalt carbonyl species
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The CoCl2/Ph(Et)2N:BH3/CO system is useful for the hydroboration and carbonylation of alkenes to obtain the corresponding dialkyl ketones. The cobalt carbonyl species formed in situ in this way is also useful for hydroacylation-cyclisation of norbornene and for the Pauson-Khand reaction.
- Rao, M. Lakshmi Narayana,Periasamy, Mariappan
-
-
- Hydrogen bonding Part 44 1Thermodynamics of complexation of 3,5-dichlorophenol with ketones and ethers in cyclohexane: The badger-Bauer relationship
-
Equilibrium constants for 1 : 1 hydrogen bond complexation between 3,5-dichioropheno' (DCP) and 17 ketones and 12 ethers in cyclohexane solution have been obtained by an FTIR method that takes into account both diiaerization of the acid and formation of 2 :1 complexes. Enthalpies of complexation for the same ketones and ethers have been determined by a calorimeiric method, leading to values of log K, AG, AH and AS0 for 1 :1 complexation in the 29 systems, as well as log K2 for the 2 :1 complexation between 2 mol of acid and 1 mol of base. For the ketone systems there is very little variation in the three thermodynamic parameters with alkyl substitution, but for the ethers there are systematic variations depending on the alkyl substituent or if the ethers are cyclic. Values of the OH stretching frequency in the DCP complexes with the ketones and ethers in cyclohexane have been obtained. The band shapes for the DCP-ketone complexes are very asymmetric, possibly due to the presence of stereoisomeric complexes, but the VOH band for DCP-ether complexes is symmetric and very suitable for the evaluation of any relationship between v()H and A/f. It is found that for the complexation of DCP with the 12 aliphatic ethers in cyclohexane, there is almost no connection between the calorimetrically determined AH° values and values of AvOH.
- Abraham, Michael H.,Prior, David V.,Schulz, Ronald A.,Morris, Jeffrey J.,Taylor, Peter J.
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p. 879 - 885
(2007/10/03)
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- Nickel catalyzed electrosynthesis of ketones from organic halides and metal carbonyls
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Ketones can be easily obtained by electroreduction in an undivided cell of an organic halide-metal carbonyl mixture using a Ni-bpy catalytic system in DMF (bpy = 2,2'-bipyridine). The process is especially well convenient for primary benzyl and alkyl halides.
- Dolhem,Ocafrain,Nedelec,Troupel
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p. 17089 - 17096
(2007/10/03)
-
- Cathodic carbonylation. Synthesis of aliphatic aldehydes using an electroreductively generated iron-carbonyl anion
-
Alkyl halides are electroreductively coupled with pentacarbonyliron to generate the acyliron complexes. After hydrolytic work-up, these anionic acyl compounds produce aldehydes in good yields. The best results were obtained with the bromide as starting halide. The first step in the formation of acyliron complexes is the direct cathodic reduction of [Fe(CO)5] to the anionic species. Synthetic and mechanistic aspects of the reaction are discussed.
- Yoshida, Kunihisa,Kuwata, Hideki
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p. 1873 - 1877
(2007/10/03)
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- New Electrochemical Synthesis of Ketones from Organic Halides and Carbon Monoxide
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The dissolution of a stainless steel anode provides catalytic nickel species which enable the efficient synthesis of ketones by electrolysis of organic halides in DMF in the presence of bipyridine and carbon monoxide.
- Ocafrain, Maitena,Devaud, Marguerite,Troupel, Michel,Perichon, Jacques
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p. 2331 - 2332
(2007/10/02)
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- Synthesis of Dialkyl Ketones from Alkenes Using Ph(Et)2N:BH3/CoCl2/CO Reagent System
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Reaction of alkenes with Ph(Et)2N:BH3/CoCl2/Co in THF followed by oxidation gives the corresponding dialkyl ketones.
- Rao, Maddali L. N.,Periasamy, Mariappan
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p. 9069 - 9070
(2007/10/02)
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- Acetal-induced cleavage of carbon-carbon bond of MEM ethers of (E)-4-alkyl-1-trimethylsilyl-1-alken-4-ols providing ketones
-
Treatment of methoxyethoxymethyl (MEM) ether of (E)-4-hexyl-1-trimethylsilyl-1-decen-4-ol with titanium(IV) chloride at -78°C afforded 7-tridecanone in 92% yield under cleavage of carbon-carbon bond. The new method was applied to the conversion of epoxides into ketones.
- Horiuchi, Yoshihiro,Taniguchi, Masahiko,Oshima, Koichiro,Utimoto, Kiitiro
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p. 7977 - 7980
(2007/10/02)
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- Mercury-Photosensitized Sulfination, Hydrosulfination, and Carbonylation of Hydrocarbons: Alkane and Alkene Conversion to Sulfonic Acids, Ketones, and Aldehydes
-
Mercury-photosensitized sulfination of alkanes, RH, with SO2 forms sulfinic acids (RSOOH) and sulfinate esters (RSOOR) in high conversion and yield; oxidation of the mixture produces RSO2OH in high yield.Mercury-photosensitized hydrosulfination of alkenes with H2 and SO2 gives RSO2OH after oxidative workup.Mercury-photosensitized carbonylation of alkanes with CO gives RCHO and R2CO.
- Ferguson, Richard R.,Crabtree, Robert H.
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p. 5503 - 5510
(2007/10/02)
-
- Direct Synthesis of Sulfines by Oxidation of Enethiolizable Thioketones
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Reaction of enethiolizable thioketones 2 with one equivalent of meta-chloroperoxybenzoic acid affords quantitatively the corresponding E sulfines 1.In contrast to literature expectations, direct synthesis of aliphatic sulfines by oxidation of thiocarbonyl compounds is thus possible; no divinyl disulfide 4 has been formed.
- Nocher, Anne Marie Le,Metzner, Patrick
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p. 747 - 750
(2007/10/02)
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- Recent Synthetic Developments in Thiocarbonyl Chemistry
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Direct oxidation of enethiolizable thioketones and dithioesters with a peroxycarboxylic acid affords the corresponding sulfines quantitatively.This observation stands in contrast with literature expectations, stating that this reaction would lead to divinyl disulfides.The oxidation shows a high stereoselectivity: delivery of the oxygen proceeds from the side opposite to the alkylthio group of dithioesters and from the side opposite to the more hindered substituent in the case of thioketones.The thermal stability of these sulfines was studied and a novel rearrangementwas observed.The second part of this report deals with the thio-Claisen rearrangement of precursors bearing a chiral centre adjacent to the pericyclic nucleus and its use for stereocontrol in the acyclic series.This thermally facile transposition leads to allylated dithioesters with good to excellent yields.A high diastereomeric selectivity was obtained in a number of cases involving either a steric effect with alkyl groups on the chiral centre or a noteworthy electronic effect when this centre bears a heteroatomic group.It was also carried out in the homochiral series.A favoured conformation and approach model is proposed to explain the formation of syn isomers.
- Metzner, Patrick
-
-
- Triethylborane Induced Selective 1,4-Reduction of α,β-Unsaturated Carbonyl Compounds with Triphenyltin Hydride or Tributyltin Hydride
-
Reduction of α,β-unsaturated ketones and esters with triphenyltin hydride or tributyltin hydride in the presence of triethylborane has been studied.Whereas the reaction of α,β-unsaturated ketones (R1CH=CHCOR2) with triphenyltin hydride provided the corresponding saturated ketones (R1CH2COR2), treatment of α,β-unsaturated ester (PhCH=CHCOOMe or CH3CH=CHCOO-n-C6H13) afforded an adduct (PhCH2CH(SnPh3)COOMe or CH3CH(SnPh3)CH2COO-n-C6H13).
- Nozaki, Kyoko,Oshima, Koichiro,Utimoto, Kiitiro
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p. 2585 - 2587
(2007/10/02)
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- Carbonylation of R2BI in the presence of NaCo(CO)4 and Na2Fe(CO)4: A simple synthesis of dialkyl ketones
-
Reaction of NaCo(CO)4 with R2BI under carbon monoxide at atmospheric pressure at room temperature readily gives the dialkyl ketones in good yields (61-85 percent) after H2O2/OH- oxidation.
- Devasagayaraj, A.,Rao, Narayana M. Lakshmi,Periasamy, M.
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p. 147 - 150
(2007/10/02)
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- Electrosynthesis of symmetrical ketones from organic halides and carbon dioxide catalysed by 2,2'-bipyridine-nickel complexes
-
The electrochemical reduction of 1 2,2'-bipyridine-nickel complex, in the presence of carbon dioxide in N-methylpyrrolidone or dimethylformamide as solvent gives the corresponding nickel(0) complex associated with two molecules of CO.Oxidative addition of an alkyl halide to this complex, followed by an internal CO shift and reductive elimination, leads to the formation of a symmetrical ketone in high yield along with nickel(II), whereas aryl or vinyl halides mainly give acyl derivatives.The nickel(0) species is electrochemically regenerated, thus giving rise to an efficient catalytic process.The possible mechanism of these reactions is discussed
- Garnier, L.,Rollin, Y.,Perichon, J.
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p. 347 - 358
(2007/10/02)
-
- Synthesis of Some New Polynuclear Compounds by Cycloaddition Reaction
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A large number of 7,9-disubstituted derivatives (I) of cyclopentacenaphthylene-8(H)-one and 2,5-disubstituted derivatives (II) of 3,4-diphenylcyclopentadienone have been synthesized by condensing acenaphthaquinone and benzil separately with suitable 1,3-disubstituted propan-2-ones.The 3-(o- and p-methoxytolyl)cyclopentadienones (IX) have been synthesized by Friedel-Crafts reaction of appropriate methyl cresyl ethers and phenacyl chloride.These dienones have been subjected to Diels-Alder reaction with acenaphthylene and a new acetylenic dienophile (V) (whose synthesis is also described in this paper) to yield a large number of polynuclear aromatic compounds having fluoranthene and p-quaterphenyl nuclei, which have been finally characterised by elemental analyses, IR and PMR spectral data.
- Samanta, S. R.,Mukherjee, A. K.
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- LITHIUM TRIS(PHENYLTHIO)METHANE FOR THE HOMOLOGATION OF TRIALKYLBORANES: CONVENIENT SYNTHESES OF KETONES AND t-CARBINOLS
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Lithium tris(phenylthio)methane is a readily available, cheap reagent for the production of ketones and t-carbinols from trialkylboranes.The scope and limitations of the reactions are indicated as are some of its unique features.
- Pelter, Andrew,Rao, J. Madhusudhana
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- A SIMPLE SYNTHESIS OF DIALKYLKETONES FROM ALKENES VIA HYDROBORATION-CARBENOIDATION
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Hydroboration of alkenes with sodium acetoxyborohydride (NaBH3OAc) followed by carbenoidation using NaoCH3/CHCl3 sytem and oxidation with H2O2/NaOH give dialkylketones.
- Narayana, C.,Periasamy, M.
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p. 6361 - 6364
(2007/10/02)
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- α,β-Epoxy Sulfoxides as Useful Intermediates in Organic Synthesis. I. A Novel Synthesis of Dialkyl Ketones and a Synthesis of Aldehydes from Ketones by One Carbon Elongation
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Treatment of α,β-epoxy sulfoxides, prepared from 1-chloroalkyl phenyl sulfoxides with ketones or aldehydes, with sodium benzeneselenolate gives dialkyl ketones or aldehydes in good yields under mild conditions.The mechanism of this reaction and an application of this process to a formal total synthesis of dihydrojasmone are described.
- Satoh, Tsuyoshi,Kaneko, Youhei,Izawa, Takao,Sakata, Kiichi,Yamakawa, Koji
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p. 1983 - 1990
(2007/10/02)
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- IMPROVED SYNTHESIS OF ALIPHATIC KETONES BY THE REACTION OF ALKYLMERCURIC BROMIDES WITH NICKEL CARBONYL IN THE PRESENCE OF POTASSIUM IODIDE
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An improved and convenient procedure for symmetrical aliphatic ketone synthesis is described, which employs the reaction of alkylmercuric bromides with nickel carbonyl in the presence of potassium iodide.
- Ryu, Ilhyong,Ryang, Membo,Rhee, Ilsong,Omura, Haruo,Murai, Shinji,Sonoda, Noboru
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p. 1175 - 1180
(2007/10/02)
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- Hydroboration. 69. Hydroboration Characteristics of Lithium Borohydride/Ethyl Acetate in Ethyl Ether. A New System for Controlled Hydroboration of Alkenes and Alkynes
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Alkenes and alkynes, which are normally inert to lithium borohydride, are readily hydroborated by this reagent in ethyl ether in the presence of carboxylic esters at 25 deg C.Alkenes form dialkylborinates while alkynes give rise either to vinylboranates or divinylborinates, depending upon the structure and reactivity of the alkyne and the stoichiometry of the reagent.This valuable intermediates are readily transformed into other organic derivatives, thus making this controlled hydroboration procedure a practical, valuable procedure in organic synthesis.
- Brown, Herbert C.,Somayaji, Vishwanatha,Narasimhan, S.
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p. 4822 - 4827
(2007/10/02)
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- A NOVEL SYNTHESIS OF DIALKYL KETONES AND α-SULFENYLATED CARBONYL COMPOUNDS FROM α,β-EPOXY SULFOXIDES
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Treatment of α,β-epoxy sulfoides with excess sodium phenylselenide and various kinds of alkylthiolates gave dialkyl ketones and α-sulfenylated carbonyl compounds, respectively, in good yields under mild conditions.
- Satoh, Tsuyoshi,Kaneko, Youhei,Kumagawa, Takumi,Izawa, Takao,Sakata, Kiichi,Yamakawa, Koji
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p. 1957 - 1960
(2007/10/02)
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