- Hyperfine Structures of Doxyl-Labeled n-Alkyl Chains by NMR and EPR
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The proton hyperfine coupling constants in a series of n-alkyl chains with a doxyl group attached at various points from the end of the chain have been measured by NMR and EPR spectroscopies.The hyperfine structure shows no further change when the attachment point is four or more carbon-carbon bonds from the end of the chain.The high resolution afforded by 500 MHz NMR reveals small magnetic inequivalencies in the chain methylene hyperfine coupling constants located at the same distance from the attachment point.Protons in the same chain methylene group are shown to have different hyperfine coupling constants while protons on different chain methylene groups, symmetrically placed with respect to attachment point, are the same, in every case except one.EPR spectra simulated from hyperfine coupling constants derived from NMR are in excellent agreement with experiment.Inhomogeneous EPR line broadening is found to be in excellent agreement with a previously derived universal hyperfine pattern (B.L.Bales, in "Biological Magnetic Resonance" (L.J.Berliner and J.Reuben, Eds.), Vol. 8, p. 77, Plenum, New York, 1989), so no new correction procedures are necessary.Strategies for selectively deuterating n-alkyl spin probes are developed and compared with some results taken from the literature.Deuterating the chain methylene groups two to three carbon-carbon bonds from the attachment point is necessary for the maximum gain in resolution and sensitivity.
- Bales, Barney L.,Mareno, Donna,Harris, Francis L.
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Read Online
- METHOD FOR CONVERTING HYDROXYL GROUP OF ALCOHOL
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The present invention relates to: a method for converting a hydroxyl group of an alcohol; and a catalyst which makes the method possible. A method for converting a hydroxyl group of an alcohol according to the present invention is characterized by producing a compound represented by CH(R1)(R2)Nu (wherein R1, R2 and Nu are as defined below) by reacting an alcohol represented by CH(R1)(R2)OH (wherein each of R1 and R2 represents a hydrogen atom, an optionally substituted alkyl group, or the like) and a compound having an active proton, which is represented by H-Nu (wherein Nu represents a group represented by —CHX1-EWG1 or —NR3R4; X1 represents a hydrogen atom or the like; EWG1 represents an electron-withdrawing group; and each of R3 and R4 represents a hydrogen atom, an optionally substituted alkyl group, or the like), with each other in the presence of a complex of a group 7-11 metal of the periodic table and at least one solid base that is selected from the group consisting of layered double hydroxides, composite oxides and calcium hydroxide.
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Paragraph 0370
(2021/02/19)
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- MnO2as a terminal oxidant in Wacker oxidation of homoallyl alcohols and terminal olefins
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Efficient and mild reaction conditions for Wacker-type oxidation of terminal olefins of less explored homoallyl alcohols to β-hydroxy-methyl ketones have been developed by using a Pd(ii) catalyst and MnO2 as a co-oxidant. The method involves mild reaction conditions and shows good functional group compatibility along with high regio- and chemoselectivity. While our earlier system of PdCl2/CrO3/HCl produced α,β-unsaturated ketones from homoallyl alcohols, the present method provided orthogonally the β-hydroxy-methyl ketones. No overoxidation or elimination of benzylic and/or β-hydroxy groups was observed. The method could be extended to the oxidation of simple terminal olefins as well, to methyl ketones, displaying its versatility. An application to the regioselective synthesis of gingerol is demonstrated.
- Fernandes, Rodney A.,Ramakrishna, Gujjula V.,Bethi, Venkati
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p. 6115 - 6125
(2020/10/27)
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- Catalytic Wacker-type Oxidations Using Visible Light Photoredox Catalysis
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A combined palladium/photoredox catalytic system for the efficient oxidation of terminal olefins to the corresponding methyl ketones is presented. The interplay of air, water, and light leads to a protocol in which the stoichiometric oxidants required for oxidative palladium catalysis are substituted with catalytic, single-electron transfer processes. Detailed mechanistic investigations revealed the role of the key components, in situ generated species, and catalysts. A broad range of substrates was examined in homogeneous as well as heterogeneous photoredox protocols, delivering the desired products in good yields.
- Ho, Yee Ann,Paffenholz, Eva,Kim, Hyun Jin,Orgis, Benjamin,Rueping, Magnus,Fabry, David C.
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p. 1889 - 1892
(2019/03/17)
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- Highly practical and efficient preparation of aldehydes and ketones from aerobic oxidation of alcohols with an inorganic-ligand supported iodine catalyst
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Herein, we divulge an efficient protocol for aerobic oxidation of alcohols with an inorganic-ligand supported iodine catalyst, (NH4)5[IMo6O24]. The catalyst system is compatible with a wide range of groups and exhibits high selectivity, and shows excellent stability and reusability, thus serving as a potentially greener alternative to the classical transformations.
- Zhang, Mengqi,Zhai, Yongyan,Ru, Shi,Zang, Dejin,Han, Sheng,Yu, Han,Wei, Yongge
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supporting information
p. 10164 - 10167
(2018/09/13)
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- Stereoselective divergent synthesis of 1,2-aminoalcohol-containing heterocycles from a common chiral nonracemic building block
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γ-N,N-Dibenzylamino-β-hydroxysulfoxide 1 proved to be an excellent chiral building block for the synthesis of a range of 1,2-amino alcohol-containing heterocycles. Thus, 1 was converted into 4,5-disubstuted oxazolidin-2-one 4 and aminoepoxides 2 and 3. Aminoepoxide 2 proved to be an excellent precursor to access oxazolidin-2-one 5 and azetidin-3-ol 6. Finally, 2 was used as a key intermediate that allowed the development of a divergent strategy to access cis-2-methyl-6-substituted piperidin-3-ol alkaloids. (+)-Deoxocassine 7 and a C-6 ethyl analogue 8 were prepared to illustrate this approach and to demonstrate that this strategy should be adaptable to the production of other members of this alkaloid family.
- Géant, Pierre-Yves,Grenet, Erwann,Martínez, Jean,Salom-Roig, Xavier J.
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- A functionalized phosphine merit preparation of ionic liquids and its application in the hydroformylation reaction
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The invention relates to synthesis of first-class phosphorus functionalized polyether alkyl guanidinium ionic liquid, and an application of the first-class phosphorus functionalized polyether alkyl guanidinium ionic liquid in a homogeneous catalytic reaction. The functionalized ionic liquid of such class can be easily prepared by an ion exchange reaction between the polyether alkyl guanidinium ionic liquid and sulfonic acid type water soluble phosphine ligand. The designed phosphorus functionalized ionic liquid can be applied to organic reactions, including hydroformylation, hydroesterification, hydrocarboxylation and catalytic hydrogenation under the catalyzing of a transition metal; the dosage of the ionic liquid used in the catalytic reaction can be decreased; the activity of the catalytic reaction can be improved; a catalyst can be separated and cycled simply and conveniently.
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Paragraph 0077; 0078; 0079
(2017/11/08)
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- METHOD FOR PRODUCING OXIDE
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Provided is a method of oxidizing a substrate with excellent oxidizing power to yield a corresponding oxide. The method can employ a commercially available imide compound as intact as a catalyst and can produce the oxide in a high yield under mild conditions. A method for producing an oxide according to the present invention includes performing oxidation of a substrate in the presence of oxygen and ozone under catalysis of an imide compound to yield a corresponding oxide. The imide compound has a cyclic imide skeleton represented by Formula (I). In the formula, n is selected from 0 and 1; and X is selected from an oxygen atom and an —OR group, where R is selected from hydrogen and a hydroxy-protecting group.
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Paragraph 0137-0139
(2016/06/28)
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- Hypervalent Iodine as a Terminal Oxidant in Wacker-Type Oxidation of Terminal Olefins to Methyl Ketones
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A mimic of the Wacker process for C=O bond formation in terminal olefins can be initiated by a combination of the Pd(II) and hypervalent iodine reagent, Dess-Martin periodinane to generate methyl ketones. This operationally simple and scalable method offers Markovnikov selectivity, has good functional group compatibility, and is mild and high yielding.
- Chaudhari, Dipali A.,Fernandes, Rodney A.
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p. 2113 - 2121
(2016/03/15)
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- Tsuji-Wacker Oxidation of Terminal Olefins using a Palladium-Carbon Nanotube Nanohybrid
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Palladium nanoparticles supported on carbon nanotubes were used in the Tsuji-Wacker oxidation. The palladium-based nanohybrid was found to be very active in combination with cuprous chloride for the selective oxidation of terminal olefins into methyl ketones. The co-catalytic system operates under very mild and sustainable conditions (room temperature, atmospheric pressure, low catalyst loading), as opposed to previously reported catalysts, and can be recycled without any loss in activity. Give it a whack: Palladium nanoparticles supported on carbon nanotubes are used in combination with cuprous chloride for the selective Tsuji-Wacker oxidation of terminal olefins into methyl ketones. The co-catalytic system operates under very mild and sustainable conditions and can be recycled without any loss in activity.
- Donck, Simon,Gravel, Edmond,Shah, Nimesh,Jawale, Dhanaji V.,Doris, Eric,Namboothiri, Irishi N. N.
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p. 2318 - 2322
(2015/08/11)
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- Synthesis of methyl ketones from terminal olefins using PdCl 2/CrO3 system mimicking the Wacker process
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An efficient synthesis of methyl ketones from terminal olefins using PdCl2/CrO3 system mimicking the Wacker process is developed. The method shows good functional groups compatibility, no aldehyde by-products and is operationally simple. CrO3 is the sole oxidant and replaces both Cu-salts and molecular oxygen, traditionally used in this process. The method holds potential for future applications in organic synthesis.
- Fernandes, Rodney A.,Bethi, Venkati
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p. 4760 - 4767
(2014/06/24)
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- Iron(III) sulfate as terminal oxidant in the synthesis of methyl ketones via wacker oxidation
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An efficient and environmentally benign method using Fe(III) sulfate as a terminal oxidant in the synthesis of methyl ketones from terminal olefins via the Wacker process is developed. The methodology offers high selectivity for a Markonikov product, shows good functional group compatibility, involves mild reaction conditions, and is operationally simple. Fe2(SO 4)3 is the sole terminal oxidant in this process. The method holds potential for future applications in organic synthesis.
- Fernandes, Rodney A.,Chaudhari, Dipali A.
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p. 5787 - 5793
(2014/07/08)
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- Ruthenium-catalyzed self-coupling of primary and secondary alcohols with the liberation of dihydrogen
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The dehydrogenative self-condensation of primary and secondary alcohols has been studied in the presence of RuCl2(IiPr)(p-cymene). The conversion of primary alcohols into esters has been further optimized by using magnesium nitride as an additive, which allows the reaction to take place at a temperature and catalyst loading lower than those described previously. Secondary alcohols were dimerized into racemic ketones by a dehydrogenative Guerbet reaction with potassium hydroxide as the additive. The transformation gave good yields of the ketone dimers with a range of alkan-2-ols, whereas more substituted secondary alcohols were unreactive. The reaction proceeds by dehydrogenation to the ketone, followed by an aldol reaction and hydrogenation of the resulting enone.
- Makarov, Ilya S.,Madsen, Robert
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p. 6593 - 6598
(2013/07/26)
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- Deoxydehydration of glycols catalyzed by carbon-supported perrhenate
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Support group: The first heterogeneous catalyst for the deoxydehydration (DODH) of glycols into olefins is reported. A carbon-supported perrhenate material was found to catalyze the reductive conversions of styrene diol, tetradecane diol, and diethyl tartrate into their respective olefins with high chemo-, regio-, and stereoselectivity. Effective reductants for this DODH reaction include H2, alcohols, and tetralin. Copyright
- Denning, Alana L.,Dang, Huong,Liu, Zhimin,Nicholas, Kenneth M.,Jentoft, Friederike C.
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p. 3567 - 3570
(2014/01/06)
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- Mild chemo-selective hydration of terminal alkynes catalysed by AgSbF 6
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The chemo-selective hydration of a wide range of non-activated terminal alkynes catalysed by AgSbF6 under mild conditions is reported.
- Thuong, Mathieu Bui The,Mann, Andre,Wagner, Alain
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supporting information; experimental part
p. 434 - 436
(2012/01/05)
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- Regioselective hydration of alkynes by iron(III) Lewis/Bronsted catalysis
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The triflimide iron(III) salt [Fe(NTf2)3] promotes the direct hydration of terminal and internal alkynes with very good Markovnikov regioselectivities and high yields. The enhanced carbophilic Lewis acidity of the FeIII cation mediated by the weakly-coordinating triflimide anion is crucial for the catalytic activity. The iron(III) metal salt can be recycled in the form of the OPPh3/[Fe(NTf2)3] system with similar activity and selectivity. However, spectroscopic and kinetic studies show that [Fe(NTf2)3] hydrolyzes under the reaction conditions and that catalytically less active BrAonsted species are formed, which points to a Lewis/Bronsted co-catalysis. This triflimide-based catalytic system is regioselective for the hydration of internal aryl-alkynes and opens the door to a new synthetic route to alkyl ketophenones. As a proof of concept, the synthesis of two antipsychotics Haloperidol and Melperone, with general butyrophenone-like structure, is shown. Just add water! The triflimide iron(III) salt [Fe(NTf2)3] promotes the direct hydration of terminal and internal alkynes with very good Markovnikov regioselectivities and high yields (see scheme). Copyright
- Cabrero-Antonino, Jose R.,Leyva-Perez, Antonio,Corma, Avelino
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supporting information; experimental part
p. 11107 - 11114
(2012/09/22)
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- A route to "all-cis" 2-methyl-6-substituted piperidin-3-ol alkaloids from syn-(2R,1′S)-2-(1-dibenzylaminomethyl)epoxide: Rapid total synthesis of (+)-deoxocassine
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A general strategy leading to the synthesis of two cis-2-methyl-6- substituted piperidin-3-ols is described. syn-(2R,1′S)-2-(1- Dibenzylaminomethyl) epoxide (13) was used as common building block. The key step involved oxirane ring opening of 13 by the nucleophilic lithium aza-enolate of hydrazones 12a and 12b. Subsequent hydrazone hydrolysis and intramolecular reductive amination afforded the alkaloid (+)-deoxocassine and a new C-6 ethyl analogue of this substance in good yields.
- Geant, Pierre-Yves,Martinez, Jean,Salom-Roig, Xavier J.
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scheme or table
p. 62 - 65
(2012/02/01)
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- Double hydroacylation reactions of acyclic and cyclic α,β- unsaturated aldehydes
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Double or quits? double hydroacylation reactions of acyclic and cyclic α,β-unsaturated aldehydes with olefins afford ketone and diketone products, respectively. Enantiomers are formed whose absolute configurations are controlled by the order of alkene addition.
- Cha, Kyung-Mi,Lee, Hyejeong,Park, Jung-Woo,Lee, Yura,Jo, Eun-Ae,Jun, Chul-Ho
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supporting information; experimental part
p. 1926 - 1930
(2011/10/17)
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- Hydroformylation of alkenes using heterogeneous catalyst prepared by intercalation of HRh(CO)(TPPTS)3 complex in hydrotalcite
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Intercalation of HRh(CO)(TPPTS)3 complex into the interlayer space of hydrotalcite was carried out to prepare an eco-friendly heterogeneous hydroformylation catalyst. Intercalated catalyst was characterized by 31P NMR, P-XRD, FT-IR, SEM and surface area measurements. Catalytic activity of intercalated catalyst [HT(3.5)-INT] was evaluated for hydroformylation of linear alkenes of varied carbon number from C5 to C13 as well as cyclic alkenes. Selectivity of the aldehydes was observed to decrease with increase in the carbon chain length of linear alkenes. Effect of reaction parameters on catalytic activity of intercalated catalyst was studied by varying the catalyst amount, 1-hexene concentration, reaction temperature, partial pressure of carbon monoxide and hydrogen for hydroformylation of 1-hexene. The catalyst was re-cycled up to five times without significant loss in the alkene conversion and selectivity of aldehydes.
- Sharma, Sumeet K.,Parikh, Parimal A.,Jasra, Raksh V.
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experimental part
p. 153 - 162
(2010/05/01)
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- Novel synthesis of methyl ketones based on the blaise reaction
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A facile two-step synthesis of methyl ketones from alkyl nitriles via the Blaise conversion of nitriles into -keto esters and acid-mediated hydrolysis followed by decarboxylation of the resulting -keto esters is described. Copyright Taylor & Francis Group, LLC.
- Rao, H. Surya Prakash,Padmavathy,Vasantham,Rafi, Shaik
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experimental part
p. 1825 - 1834
(2009/10/02)
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- Electrochemical generation of cationic Pd catalysts and application to Pd/TEMPO double-mediatory electrooxidative Wacker-type reactions
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We have developed an electrooxidative method for generating cationic palladium complexes [Pd(CH3CN)4][X]2 (X = BF4, PF6, and ClO4) from Pd(OAc)2 and several electrolytes bearing X groups in CH3CN. The system could be integrated into an electrochemical Wacker-type reaction. In the presence of a catalytic amount of TEMPO, the reaction proceeded smoothly to give the corresponding methyl ketones. Copyright
- Mitsudo, Koichi,Kaide, Takashi,Nakamoto, Eriko,Yoshida, Kenta,Tanaka, Hideo
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p. 2246 - 2247
(2007/10/03)
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- Solvent-free chelation-assisted catalytic C-C bond cleavage of unstrained ketone by rhodium(I) complexes under microwave irradiation
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A highly efficient C-C bond cleavage of unstrained aliphatic ketones bearing β-hydrogens with olefins was achieved using a chelation-assisted catalytic system consisting of (Ph3P)3RhCl and 2-amino-3-picoline by microwave irradiation under solvent-free conditions. The addition of cyclohexylamine catalyst accelerated the reaction rate dramatically under microwave irradiation compared with the classical heating method.
- Ahn, Jeong-Ae,Chang, Duck-Ho,Young, Jun Park,Ye, Rim Yon,Loupy, Andre,Jun, Chul-Ho
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- Dendrimer-Palladium complex catalyzed oxidation of terminal alkenes to methyl ketones
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Silica-supported polyamidoamine (PAMAM) dendrimers with different spacer lengths were prepared. After the introduction of diphenylphosphino groups, complexation to dibenzylidenepalladium(0) gave the desired silica-supported dendrimer - palladium catalyst complexes G0 to G4-C2-Pd. These catalysts showed activity towards the oxidation of terminal alkenes to methyl ketones. A dependence of catalytic activity on the spacer length of the diamine in PAMAM was observed.
- Zweni, Pumza P.,Alper, Howard
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p. 849 - 854
(2007/10/03)
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- Selective Wacker-type oxidation of terminal alkenes and dienes using the Pd(II)/molybdovanadophosphate (NPMoV)/O2 system
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Selective Wacker-type oxidation of long-chain terminal alkenes to methylketones was successfully achieved by using Pd(OAc)2/molybdovanadophosphate (NPMoV)/O2 system. The selectivity of the reaction increased by slow addition of the alkenes to the catalytic solution. The oxidation of α,ω-dienes was also examined, and the selectivity of the oxidation was found to depend on the chain length of the dienes used.
- Yokota, Takahiro,Sakakura, Aki,Tani, Masayuki,Sakaguchi, Satoshi,Ishii, Yasutaka
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p. 8887 - 8891
(2007/10/03)
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- Palladium(II)-catalyzed oxidation of terminal alkenes to methyl ketones using molecular oxygen
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Palladium(II) acetate catalyzes the aerobic oxidation of terminal alkenes in toluene into the corresponding methyl ketones in the presence of a catalytic amount of pyridine using propan-2-ol as a reductant and molecular oxygen as an oxidant. Two catalytic cycles sharing a Pd(II)-OOH species are proposed. One is the formation of a Pd(II)-H species in the oxidation of propan-2-ol to acetone, followed by reaction with molecular oxygen to give a Pd(II)-OOH species, and the other is peroxypalladation of an alkene with the Pd(II)-OOH species produced to afford a methyl ketone in the presence of H2O2 produced by the former catalytic cycle. The Royal Society of Chemistry 2000.
- Nishimura, Takahiro,Kakiuchi, Nobuyuki,Onoue, Tomoaki,Ohe, Kouichi,Ucmura, Sakae
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p. 1915 - 1918
(2007/10/03)
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- Metalloporphyrin-catalyzed regioselective rearrangement of monoalkyl-substituted epoxides into aldehydes
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Iron(III) tetraphenylporphyrin, Fe(tpp)OTf, is an efficient catalyst for the regioselective rearrangement of simple monoalkyl-substituted epoxides into the corresponding aldehydes.
- Suda, Kohji,Baba, Kenji,Nakajima, Shin-ichiro,Takanami, Toshikatsu
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p. 7243 - 7246
(2007/10/03)
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- A Very Useful and Efficient Wacker Oxidation of Higher α-Olefins in the Presence of Per(2,6-di-O-methyl)-β-Cyclodextrin
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Oxidation of higher α-olefins (C8-C16) in a two phase system with a multicomponent catalytic system, i.e.PdSO4/H9PV6Mo6O40/CuSO4 and per(2,6-di-O-methyl)-β-cyclodextrin gives the corresponding 2-ketones in high yields ( >90 percent)
- Monflier, Eric,Tilloy, Sebastien,Fremy, Georges,Barbaux, Yolande,Mortreux, Andre
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p. 387 - 388
(2007/10/02)
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- Telluroxide Elimination by Oxidation of Alkyl Aryl Tellurides: Remarkable Effect of Added Triethylamine
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Treatment of various alkyl phenyl tellurides with 1-2 mol equiv. of m-chloroperbenzoic acid in diethyl ether in the presence of triethylamine at 25 deg C for 2 h affords the corresponding alkenes highly selectively in fair to good yields.From stereochemical studies using erythro- and threo-phenyl 3-phenylbutan-2-yl tellurides as substrates it was revealed that although Et3N partly faciliates E2 elimination of the telluroxide, the main reaction course is the telluroxide syn-elimination (Ei elimination).Without the addition of Et3N the elimination was quite slow in many cases, and in fact the compounds derived from the addition of m-chlorobenzoic acid to tetradecyl and cyclohexyl phenyl telluroxides were isolated, the pyrolysis (ca. 250 deg C) of which afforded tetradec-1-ene and cyclohexene, respectively.A 2-pyridyltelluro moiety was revealed for the first time to be a better leaving group than a phenyltelluro moiety in telluroxide elimination.
- Nishibayashi, Yoshiaki,Komatsu, Naoki,Ohe, Kouichi,Uemura, Sakae
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p. 1133 - 1138
(2007/10/02)
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- Inhibitors of acyl-CoA:cholesterol acyltransferase. 5. Identification and structure-activity relationships of novel β-ketoamides as hypocholesterolemic agents
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A study of structure-activity relationships of substituted β-ketoamide ACAT inhibitors I and II was performed. The results of this study suggest that whereas the β-keto group was tolerated with no loss in activity, β- hydroxy and oxime moieties led to significantly reduced activity in vitro and in vivo. The most potent inhibitor from the acyclic series (I) (11, IC50 = 0.006 μM) contained a C-13 alkyl chain. This compound reduced plasma total cholesterol by 38% and 66% at 3 and 30 mg/kg, respectively, in cholesterol- fed rats. Dimethylation α to the anilide core (5) and subsequent N- methylation of the amide NH (6) decreased in vitro potency significantly. It was also found that high potency was retained with inhibitors which incorporated the carbonyl into a lactam ring (II).
- Augelli-Szafran,Blankley,Roth,Trivedi,Bousley,Essenburg,Hamelehle,Krause,Stanfield
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p. 2943 - 2949
(2007/10/02)
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- SAMARIUM(II) IODIDE PROMOTED RADICAL RING OPENING REACTIONS OF CYCLOPROPYL KETONES
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Radical ring opening reactions of cyclopropyl ketones mediated by samarium(II) iodide-induced single electron transfer have permitted the elaboration of a tandem rearrangement cyclisation strategy.The resultant samarium enolates may be effectively quenched on oxygen or carbon by electrophiles.Key Words: Samarium(II) Iodide Reduction; Cyclopropylcarbinyl Radical Rearrangement; Cyclopropyl Ketone; Radical Cyclisation; Samarium Enolate.
- Batey, Robert A.,Motherwell, William B.
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p. 6649 - 6652
(2007/10/02)
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- Samarium(II) iodide promoted radical ring opening reactions of cyclopropyl ketones
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Radical ring opening reactions of cyclopropyl ketones mediated by samarium(II) iodide-induced single electron transfer have permitted the elaboration of a tandem rearrangement cyclisation strategy. The resultant samarium enolates may be effectively quenched on oxygen or carbon by electrophiles.
- Batey,Motherwell
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p. 6211 - 6214
(2007/10/02)
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- A palladium(II) catalyst for oxygenation of terminal olefins with molecular oxygen
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Oxidation of terminal olefins with molecular oxygen by a catalyst system consisting of acetoxime, CuCl, and PdCl2 in anhydrous acetone gives the corresponding methyl ketones.
- Hosokawa, Takahiro,Takahashi, Tsukasa,Ohta, Toshiyuki,Murahashi, Shin-ichi
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- Cyclodextrin-Palladium Chloride.New Catalytic System for Selective Oxidation of Olefins to Ketones
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Terminal olefins are oxidized to ketones in high yields under mild conditions using palladium chloride and cyclodextrins as catalysts in two-phase systems; cyclodextrins show substrate selectivity.
- Harada, Akira,Hu, Ying,Takahashi, Shigetoshi
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p. 2083 - 2084
(2007/10/02)
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- TELLUROXIDE ELIMINATION BY DIRECT OXIDATION OF ALKYL PHENYL TELLURIDE
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Treatment of sec-alkyl phenyl tellurides, except for the cyclohexyl system, with m-chloroperbenzoic acid(MCPBA) in diethyl ether readily afforded the corresponding olefins in good yields presumably via telluroxide elimination together with small amounts of alcohols and ketones.In the pri-alkyl and cyclohexyl cases the adducts between MCPBA and the tellurides were isolated as stable organotellurium(IV) compounds which gave similar elimination products by neat pyrolysis at 220-250 deg C.
- Uemura, Sakae,Ohe, Kouichi,Fukuzawa, Shin-ichi
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p. 895 - 898
(2007/10/02)
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- ALDEHYDE AND KETONE SYNTHESES USING METHYLTHIOMETHYL p-TOLYL SULFONE
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Methylthiomethyl p-tolyl sulfone (1) was conveniently alkylated to give mono- and dialkylated products (2 and 4).Reaction conditions for the transformation of 2 and 4 into aldehydes (3) and ketones (5), respectively, were exploited.
- Ogura, Katsuyuki,Ohtsuki, Kazuo,Nakamura, Masami,Yahata, Nobuhiro,Takahashi, Kazumasa,Iida, Hirotada
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p. 2455 - 2458
(2007/10/02)
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- Microbial Oxidation of Tetradecanols and Related Substances in Organic Solvents
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Microbial oxidations of n-tetradecane, tetradecanols and tetradecanoic acid were investigated by using intact cells of Corynebacterium equi, a hydrocarbon-assimilating bacterium, in an aqueous phase and organic solvents.The bacterial cells were hydrophobic and could be well dispersed in all organic solvents employed to give homogeneous reaction mixtures, and among them, isooctane was found to be the best for the reaction. n-Tetradecane and tetradecanoic acid were completely oxidized in the agueous phase, but not in isooctane.In contrast, 1-tetradecanol was oxidized much more readily in isooctane than in the aqueous phase, and an oxidation product identified as myristyl myristate was accumulated in isooctane at the conversion rate of 80percent. 2-Tetradecanol was also readily oxidized in isooctane, and 2-tetradecanone was obtained at the conversion rate of nearly 100percent.Similar results were obtained when toluene and n-hexane were used as the solvent in place of isooctane, while no reaction was observed when chloroform was employed.
- Takazawa, Yoshiharu,Sato, Seigo,Takahashi, Joji
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p. 2489 - 2496
(2007/10/02)
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- New Aspects of the Telluroxide Elimination. A Facile Elimination of sec-Alkyl Phenyl Telluroxide Leading to Olefins, Allylic Alcohols, and Allylic Ethers
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The utility of the telluroxide for olefin synthesis, a reaction which previously appeared to be of little value, is described.Treatment of sec-alkylphenyltellurium dibromides, except for the cyclohexyl system, with aqueous NaOH at room temperature affords olefins, allylic alcohols, and/or allylic ethers in high yields presumably via the formation of sec-alkyl phenyl telluroxides and their facile telluroxide elimination.As to the formation of linear olefins, more preference for elimination toward the less substituted carbon was observed than the selenoxide and sulfoxide eliminations.In the cyclododecyl case only trans-cyclododecene was formed as an olefin component in a sharp contrast to the selenoxide elimination that affords a 1:1 mixture of cis and trans isomers.On the contrary, in the n-alkyl and cyclohexyl cases the corresponding telluroxides are stable compounds that afford similar elimination products including vinylic ethers only by neat pyrolysis at temperatures above 200 deg C.
- Uemura, Sakae,Fukuzawa, Shin-ichi
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p. 2748 - 2752
(2007/10/02)
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- NOVEL CONVERSION OF A KETONE DIMETHYL DITHIOACETAL S,S-DIOXIDE TO THE CORRESPONDING KETONE AND ITS APPLICATION TO SYNTHESIS OF ACYCLIC AND CYCLIC KETONES
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A ketone dimethyl dithioacetal S,S-dioxide was easily hydrolyzed with hydrochloric acid in refluxing methanol and this transformation was applied to a new method for making acyclic and cyclic ketones by the use of formaldehyde dimethyl dithioacetal S,S-dioxide.
- Ogura, Katsuyuki,Suzuki, Michiyo,Watanabe, Jun-ichi,Yamashita, Mitsuo,Iida, Hirotada,Tsuchihashi, Gen-ichi
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p. 813 - 814
(2007/10/02)
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- Mode of Metabolism of 1-Tetradecene by Candida Yeasts and Citrates Production
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Metabolic pathways for the oxidation of 1-tetradecene by Candida lipolytica were investigated and compared with those for Candida tropicalis in oder to elucidate the difference in the productivity of citrates reported in the previous paper.No difference was found in the pathways for the initial stage of oxidation of 1-tetradecene between the two strains, indicating that the difference in the productivity of citrates is not attributable to the metabolic pathways.The metabolic rate of 1-tetradecene with C. lipolytica was found to be much lower than that with C. tropicalis.The production of citrates was much enhanced in the presence of surfactants which were known to be stimulative for microbial metabolism of hydrocarbons and 11-15 g/liters was attained on the 6th day of cultivation.
- Terasawa, Masato,Takahashi, Joji
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p. 2433 - 2442
(2007/10/02)
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