- Study of the oxidative esterification of furfural catalyzed by Au25(glutathione)18 nanocluster deposited on zirconia
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Au/ZrO2 catalyst prepared from Au25(SG)18 nanoclusters (SG stands for glutathione) deposited on ZrO2 has shown to be an efficient system for the oxidative esterification of furfural with methanol. The influence of the supported nanoclusters was studied and showed that partial calcination of the supported nanoclusters at 300 °C was sufficient for a quantitative formation of methyl-2-furoate even in the absence of a base. In the presence of 0.27 mol% of Au, initial activities up to 250 h?1 were obtained at 100 °C under 6 bar of O2. The reactivity was extended to the oxidative esterification of furfuryl alcohol and the formation of various products and intermediates was discussed.
- Shahin, Zahraa,Rataboul, Franck,Demessence, Aude
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- A selective oxidative valorization of biomass-derived furfural and ethanol with the supported gold catalysts
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The oxidative upgrading of renewable furfural (FUR) and ethanol is an important way to produce high-quality liquid fuel and value-added furanic derivatives. In this work, a series of supported Au catalysts were prepared using the colloid-immobilization technique, and further employed for catalytic oxidative condensation of FUR with ethanol in the presence of molecular oxygen. It is found that, with Au@CaO as the catalyst, 85.9% conversion of FUR and 81.8% selectivity of the product furan-2-acrolein were achieved in the absence of any homogeneous basic additive. The effects of different reactions such as reaction time, temperature and catalyst amount were explored in detail. Also, the influences of calcination temperature and amount of protective agent during the preparation of catalyst were investigated. According to the characterization results of catalyst, it is concluded that the synergistic effect of metallic Au and basic site of CaO support plays a significant role on the selective oxidative condensation. At last, a possible reaction mechanism is proposed based on the catalytic principle and experimental results.
- Gao, Yiqi,Tong, Xinli,Zhang, Haigang
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p. 238 - 245
(2019/06/18)
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- Enantioselective Aldol Addition of Acetaldehyde to Aromatic Aldehydes Catalyzed by Proline-Based Carboligases
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Aromatic β-hydroxyaldehydes, 1,3-diols, and α,β-unsaturated aldehydes are valuable precursors to biologically active natural products and drug molecules. Herein we report the biocatalytic aldol condensation of acetaldehyde with various aromatic aldehydes to give a number of aromatic α,β-unsaturated aldehydes using a previously engineered variant of 4-oxalocrotonate tautomerase [4-OT(M45T/F50A)] as carboligase. Moreover, an efficient one-pot two-step chemoenzymatic route toward chiral aromatic 1,3-diols has been developed. This one-pot chemoenzymatic strategy successfully combined a highly enantioselective aldol addition step catalyzed by a proline-based carboligase [4-OT(M45T/F50A) or TAUT015] with a chemical reduction step to convert enzymatically prepared aromatic β-hydroxyaldehydes into the corresponding 1,3-diols with high optical purity (e.r. up to >99:1) and in good isolated yield (51-92%). These developed (chemo)enzymatic methodologies offer alternative synthetic choices to prepare a variety of important drug precursors.
- Biewenga, Lieuwe,Charnock, Simon J.,Guo, Chao,Poelarends, Gerrit J.,Saifuddin, Mohammad,Saravanan, Thangavelu
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p. 2522 - 2527
(2020/03/11)
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- Selective carbon-chain increasing of renewable furfural utilizing oxidative condensation reaction catalyzed by mono-dispersed palladium oxide
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A novel carbon-chain increasing valorization of furfural (FUR), a cheap bio-based platform compound, has been successfully performed via the catalytic oxidative condensation process with mono-dispersed palladium oxide catalyst. For the reaction of furfural, n-propanol and O2, the PdO?TiO2 exhibited a prominent catalytic activity in which a 77.8% conversion of FUR with 89.2% selectivity of 3-(furan-2-yl)-2-methylacrylaldehyde was obtained. Based on the XRD, SEM, TEM, HRTEM, XPS, and UV–vis results of catalysts, it was concluded that high activity is associated with particle size, uniform distribution of palladium oxide and surface area of the support. Moreover, the recycling experiments confirmed that mono-dispersed palladium oxide catalyst was stable, in which it still kept a good catalytic performance after being recycled for five times. This provided a new route for the selective transformation of the hemicellulose-derived platform compounds.
- Tong,Zhang, Zhenya,Gao, Yiqi,Zhang, Yue,Yu, Linhao,Li, Yongdan
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- A method for utilizing high-efficiency catalytic oxidation of furfural and fatty alcohol preparation furan for fluoro method
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The invention discloses a method for preparing furyl aldehyde by using efficient catalytic oxidation of furfural and fatty alcohol. Furyl aldehyde is prepared from furfural as a substrate and supported nano gold as a catalyst. The method comprises the following specific steps: dissolving furfural into an organic solvent, adding to the supported nano gold and an assistant, and reacting at 25-170 DEG C for 1-15 hours in a 0.01-05MPa oxygen atmosphere under the condition that the stirring speed is 100-5,000r/min; and carrying out selective catalytic oxidation on furfural and fatty alcohol through the supported nano gold, so as to prepare furyl aldehyde. The preparation method is simple and easy to operate, generates few by-products and is friendly to environment. A supported nano gold catalyst is adopted, is mild in condition, good in catalysis effect, easy to recover, and can be repeatedly used; the supported nano gold catalyst can be used for efficiently catalyzing oxidation of furfural with high selectivity to generate furyl aldehyde; and the product is easy to separate, the production cost is low, and technical and economic effects are remarkable, and therefore the method has a good application prospect.
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Paragraph 0012; 0013; 0015; 0017; 0019
(2018/04/20)
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- A regulatable oxidative valorization of furfural with aliphatic alcohols catalyzed by functionalized metal-organic frameworks-supported Au nanoparticles
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The oxidative upgrading of furfural (FUR) and aliphatic alcohols is an important way to produce desirable precursor of jet fuel or value-added furanic compound. Therein, developing a highly active catalytic system with switchable product selectivity still remains a challenge. In this work, we report a novel strategy on regulating the oxidative condensation and oxidative esterification of FUR with aliphatic alcohol in the presence of molecular oxygen. Firstly, Au@UiO-66 is prepared using different methods and employed as the catalyst for the oxidative valorization of FUR with methanol. It is found that the impregnation-reduction-H2 (I-H) method is the best where a 100% selectivity of methyl-2-furoate with a complete conversion was obtained using Au@UiO-66 as catalyst. Then, a series of metal-organic frameworks (MOFs) supported Au nanoparticles (Au@UiO-66-X) such as Au@UiO-66, Au@UiO-66-NH2, Au@UiO-66-NO2, Au@UiO-66-COOH and Au@UiO-66-NH3Cl have been prepared with I-H method and employed for oxidative valorization of furfural with ethanol. Experimental results showed that, in “FUR-ethanol-O2” system, the Au@UiO-66-X can efficiently regulate the oxidative condensation and oxidative esterification as two competitive reaction pathways. With Au@UiO-66-COOH as the catalyst, the oxidative condensation process is dominant in which 84.1% selectivity of furan-2-acrolein is attained; Meanwhile, the Au@UiO-66 is beneficial to the occurrence of oxidative esterification and generation of ethyl-2-furoate. At last, based on the catalyst characterization and the numerous control experiments, a possible catalytic reaction mechanism for conversion of FUR is proposed.
- Ning, Liangmin,Liao, Shengyun,Liu, Xuguang,Guo, Pengfei,Zhang, Zhenya,Zhang, Haigang,Tong, Xinli
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- Versatile catalysis of iron: Tunable and selective transformation of biomass-derived furfural in aliphatic alcohol
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An iron-catalyzed efficient valorization of biomass-derived furfural (FUR) in aliphatic alcohols is developed in which product selectivity can be simply regulated by varying the gas atmosphere. In the presence of molecular oxygen, there is oxidative condensation of FUR with ethanol, and the obtained product is furan-2-acrolein in a "FUR-ethanol-O2" system. Under suitable conditions, the conversion of FUR and selectivity of furan-2-acrolein are 84.2% and 82.7%, respectively. In the presence of H2, the selective hydrogenation of FUR is achieved, and the main product is furfuryl alcohol in a "FUR-ethanol-H2" system. Under optimal conditions, a 99.9% conversion of FUR and 93.6% selectivity of furfuryl alcohol are attained. This provides an economic, green and sustainable method for the utilization of biomass-based platform compounds in the chemical industry.
- Zhang, Zhenya,Tong, Xinli,Zhang, Haigang,Li, Yongdan
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p. 3092 - 3100
(2018/07/13)
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- Secondary amine-catalyzed [3 + 3] benzannulation to access polysubstituted benzenes through iminium activation
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An organocatalytic [3 + 3] benzannulation to access polysubstituted benzenes from readily available α,β-unsaturated aldehydes and 1,3-bis(phenylsulfonyl)propene or 4-sulfonylcrotonates is described. The key reaction step is considered to be the iminium ac
- Jiang, Lin,Li, Hang,Zhou, Jiang-Feng,Yuan, Ming-Wei,Li, Hong-Li,Chuan, Yong-Ming,Yuan, Ming-Long
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supporting information
p. 336 - 343
(2018/02/09)
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- Efficient and selective transformation of biomass-derived furfural with aliphatic alcohols catalyzed by a binary Cu-Ce oxide
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The efficient transformation of furfural (FUR) with aliphatic alcohols to achieve the carbon-chain growth has been developed using a binary Cu-Ce oxide as the catalyst. In the presence of molecular oxygen, the tandem oxidative condensation of FUR with n-propanol is successfully performed, in which an 85.4% conversion of FUR in 95.3% selectivity of 3-(furan-2-yl-)-2-methylacryaldehyde was obtained. The effects of different Cu/Ce ratios and base additives were investigated in detail. As a result, it is found that the CuO-CeO2 (1: 9) catalyst is optimal and potassium carbonate is a suitable additive. Next, the recycling of CuO-CeO2 catalyst was tested and there is no obvious activity loss after being reused five times. Moreover, the oxidative condensation of FUR with various aliphatic alcohols including ethanol, isopropanol, n-butanol and n-hexanol was studied where the long chain alcoholic molecule hinders the proceeding of reaction. Finally, based on the experimental results and reaction phenomena, a possible mechanism for the oxidative condensation of FUR with n-propanol-O2 is proposed.
- Tong, Xinli,Yu, Linhao,Luo, Xuan,Zhuang, Xuli,Liao, Shengyun,Xue, Song
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p. 175 - 180
(2017/09/30)
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- One-Pot l-Proline-Mediated Stereoselective α-C(sp2)–H Fluorination of α,β-Unsaturated Aldehydes through Methoxyfluorination–Elimination
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A one-pot, two-step l-proline-mediated stereoselective α-C(sp2)–H fluorination of α,β-unsaturated aldehydes towards their corresponding (Z)-α-fluoro-α,β-unsaturated aldehydes has been developed. The first step utilises Selectfluor as a fluorinating agent in CH3NO2/MeOH forming (Z)-α-fluoro-α,β-unsaturated aldehydes and their corresponding dimethyl acetals through methoxyfluorination-elimination. In the second step, water is added to promote the hydrolytic cleavage of the dimethyl acetals. The obtained (Z)-α-fluoro-α,β-unsaturated aldehydes were smoothly reduced to the corresponding alcohols by using NaBH4.
- Zhou, Jiadi,Jiang, Xinpeng,Jin, Can,Guo, Zhicheng,Su, Bin,Su, Weike
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supporting information
p. 3631 - 3634
(2017/07/22)
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- A smart catalyst system for the valorization of renewable furfural in aliphatic alcohols
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A highly efficient and selective oxidative condensation-hydrogenation process of renewable furfural with aliphatic alcohols catalyzed by metallic platinum in a one-pot reactor is developed. A series of supported platinum catalysts including Pt/FH, Pt/H, Pt/HT, Pt/Fe3O4, Pt/Al2O3 and Pt/ZrO2 are prepared and employed for the polarization of furfural in ethanol and n-propanol. It is found that, in the presence of Pt/FH and potassium carbonate, 93.9% conversion of furfural and 67.9% selectivity to furan-2-acrolein were obtained via oxidative condensation in the furfural-ethanol-O2 (FEO) system, and 90.1% conversion of furfural and 90% selectivity to 3-(furan-2-yl-)-2-methylacrylaldehyde were obtained via oxidative condensation in the furfural-n-propanol-O2 (FPO) system. Moreover, the oxygen in the FPO system is completely replaced by molecular hydrogen to allow the further conversion of 3-(furan-2-yl-)-2-methylacrylaldehyde, while the catalytic system was kept unchanged. During this process, 87.3% conversion of 3-(furan-2-yl-)-2-methylacrylaldehyde and 73.2% selectivity to 3-(furan-2-yl-)-2-methylpropanol were obtained via a hydrogenation reaction with the Pt/FH catalyst. Moreover, several common bases as promoters were investigated in detail. All the catalysts were characterized by XRD, TEM, SEM, TPD and BET methods to reveal their catalytic nature in the reaction.
- Liu, Zonghui,Tong, Xinli,Liu, Jinbiao,Xue, Song
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p. 1214 - 1221
(2016/02/27)
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- An enantioselective three-component reaction of diazoacetates with indoles and enals by iridium/iminium co-catalysis
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The first example of chiral secondary amine and iridium(i) co-catalyzed enantioselective three-component reaction of aryldiazoacetates, indoles and enals was rationally designed and developed to afford 3-substituted indole derivatives in good yields and with moderate diastereoselectivity as well as excellent enantioselectivity. This reaction is proposed to proceed through the enantioselective trapping of iridium(i)-associated zwitterionic intermediates via selective 1,4-addtition to the chiral amine activated enals.
- Li, Mingfeng,Guo, Xin,Jin, Weifeng,Zheng, Qing,Liu, Shunying,Hu, Wenhao
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supporting information
p. 2736 - 2739
(2016/02/19)
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- Oxygenative and Dehydrogenative [3 + 3] Benzannulation Reactions of α,β-Unsaturated Aldehydes and γ-Phosphonyl Crotonates Mediated by Air: Regioselective Synthesis of 4-Hydroxybiaryl-2-carboxylates
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Regioselective synthesis of 4-hydroxybiphenyl-2-carboxylates via the base-mediated oxygenative [3 + 3] benzannulation reaction of α,β-unsaturated aldehydes and γ-phosphonyl crotonates is reported. A hydroxyl group is installed in the final product on the originally phosphorus-bound carbon via a novel oxygenative and dehydrogenative transformation. The reaction proceeds rapidly in an open flask, uses atmospheric oxygen as an oxidant, and affords good yields of substituted biaryl phenols. (Chemical Equation Presented).
- Joshi, Prabhakar Ramchandra,Nanubolu, Jagadeesh Babu,Menon, Rajeev S.
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supporting information
p. 752 - 755
(2016/03/01)
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- Au-catalyzed oxidative condensation of renewable furfural and ethanol to produce furan-2-acrolein in the presence of molecular oxygen
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A specialty chemical compound, furan-2-acrolein, can be produced from renewable feedstock via furfural. An efficient catalytic process related to oxidative condensation of furfural and ethanol using supported Au catalyst has been developed. A series of solid catalysts including Au/Al2O3, Au/CeO2, Au/Fe3O4, Au/HTc (hydrotalcite calcined) and Au/Nb2O5 are prepared and their catalytic activities in oxidative condensation of furfural with ethanol are compared. Moreover, the influence of the presence of base promoters, such as K2CO3, on Au catalyst performance is investigated. The physical properties of these catalysts are characterized by XRD, TEM, SEM, UV-vis and BET techniques. The impact of reaction variables on catalyst performance is measured. It has been found that, in the presence of Au/Al2O3 and potassium carbonate, 94.1% conversion of furfural and 75.0% selectivity to furan-2-acrolein are obtained under the conditions of 140 °C, 0.3 MPa of O2 and reaction time of 4 h.
- Tong, Xinli,Liu, Zonghui,Hu, Jianli,Liao, Shengyun
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p. 196 - 203
(2015/12/05)
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- Highly regio- And enantioselective synthesis of g,d-unsaturated amido esters by catalytic hydrogenation of conjugated enamides
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An efficient and highly regio- and enantioselective catalytic asymmetric hydrogenation of a,γ-dienamido esters to g,d-unsaturated amido esters has been achieved using Rh/ TangPhos as the catalyst. A series of γ,δ-unsaturated amido acids were furnished in excellent yields with up to 99%ee. This effective methodology was applied in the asymmetric synthesis of key intermediate of Ramipril, an ACE inhibitor.
- Min, Gao,Jing-jing, Meng,Hui, Lv,Xumu, Zhang
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supporting information
p. 1885 - 1887
(2015/02/19)
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- Rare earth triflates/chlorotrimethylsilane-promoted one-pot synthesis of enals
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Some heteroaromatic aldehydes were subjected to conditions promoting the rare earth triflates/chlorotrimethylsilane-promoted one-pot synthesis of enals. As a result, diverse α,β-unsaturated aldehydes were obtained in moderate yields.
- Kagawa, Natsuko,Sasaki, Yoshiko,Sakaguchi, Shoko,Nagatomo, Ayumi,Kojima, Hideo,Toyota, Masahiro
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p. 1581 - 1585
(2016/11/07)
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- Fukuyama reduction and integrated thioesterification/fukuyama reduction of thioesters and acyl chlorides using continuous flow
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Fukuyama reduction of thioesters has been achieved using a polymer-supported Pd[0] catalyst (Pd/XAD-4), and continuous flow conditions. The generality of this reaction is good with a range of aldehydes prepared in excellent yields. In addition, an integrated multistep thioesterfication/ Fukuyama reduction has been developed that allows acyl chlorides to be directly converted to the corresponding aldehydes. Integral to this process is the use of polymer-supported amine and isocyanate reagents to achieve thioesterification and scavenge unreacted thiol. In addition, catch-and-release purification has been employed to enable isolation of the aldehyde from silylthioether byproducts without the need for chromatographic purification.
- Asadi, Mousa,Bonke, Shannon,Polyzos, Anastasios,Lupton, David W.
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p. 2070 - 2074
(2014/06/24)
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- Combined heterogeneous metal/chiral amine: Multiple relay catalysis for versatile eco-friendly synthesis
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Herein is described a versatile and broad synergistic strategy for expansion of chemical space and the synthesis of valuable molecules (e.g. carbocycles and heterocycles), with up to three quaternary stereocenters, in a highly enantioselective fashion from simple alcohols (31 examples, 95:5 to >99.5:0.5 e.r.) using integrated heterogeneous metal/chiral amine multiple relay catalysis and air/O2 as the terminal oxidant. A novel highly 1,4-selective heterogeneous metal/amine co-catalyzed hydrogenation of enals was also added to the relay catalysis sequences. Relay switch: A versatile strategy for expansion of chemical space and the synthesis of valuable molecules, having up to three quaternary stereocenters, in a highly enantioselective fashion from simple alcohols is described. The method employs integrated heterogeneous metal/chiral amine multiple relay catalysis and air/O2 as the terminal oxidant.
- Deiana, Luca,Jiang, Yan,Palo-Nieto, Carlos,Afewerki, Samson,Incerti-Pradillos, Celia A.,Verho, Oscar,Tai, Cheuk-Wai,Johnston, Eric V.,C?rdova, Armando
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supporting information
p. 3447 - 3451
(2014/04/03)
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- Multistep organocatalysis for the asymmetric synthesis of multisubstituted aldehydes from allylic alcohols
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The combination of a copper complex and a chiral amine organocatalyst induces the formation of multifunctionalized aldehydes from aromatic and aliphatic allylic alcohols. Reactions occur with excellent levels of enantioselectivity, under environmentally benign conditions, and without involving stoichiometric amounts of chemical oxidants for the oxidation of the allylic alcohols or rigorous reaction conditions for transition-metal catalysis.
- Ho, Xuan-Huong,Oh, Hyun-Ji,Jang, Hye-Young
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p. 5655 - 5659
(2012/11/13)
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- Oxidative and enantioselective cross-coupling of aldehydes and nitromethane catalyzed by diphenylprolinol silyl ether
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Synthetically important β-substituted γ-nitro aldehydes have been synthesized with excellent enantioselectivity by the cross-coupling reaction of β-aryl substituted aldehydes or Y γ-unsaturated aldehydes and nitromethane using 2,3-dichloro-5,6-dicyanoquinone (DDQ) and diphenylprolinol silyl ether as an oxidant and catalyst, respectively (see scheme; TMS=trimethylsilyl).
- Hayashi, Yujiro,Itoh, Takahiko,Ishikawa, Hayato
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supporting information; experimental part
p. 3920 - 3924
(2011/05/15)
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- ANALGESIC 5, 9 - METHANOCYCLOOCTA (b) PYRIDIN - 2 (1H) - ONE DERIVATIVES, THEIR PREPARATION METHOD AND USE
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Compounds represented by the Formula I or salts, hydrates thereof, wherein R1, R8, R11 and R12 are H or C1-4 hydrocarbonyl respectively; R2, R3, R6 and R7 are H, halogen or C1-4 hydrocarbonyl respectively; R4 is C1-6 hydrocarbonyl or Ar; or =CR4R3 is cyclopentylidene, cyclohexylidene, 1-methylpiperidyl-4-idene or indenyl-1-idene; R5 is H, 1-4 same or different F, Cl, Br, CF3, R9, OR9, NR9R10, NO2, CN, COOR9, O2CR9, CONR9R10, NR9C(O)R10, heterocyclic, aryl or groups represented by the Formula II respectively; R9 and R10 are H or C1-6 hydrocarbonyl; Ar is aromatic ring; m is 0, 1 or 2; n is 0, 1, 2, 3 or 4, for treating mammal pain, functional painful syndrome, organic painful syndrome or tissue painful syndrome, and their preparation method.
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Page/Page column 15
(2009/04/23)
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- 1,4-benzoquinone: A new selective reagent for oxidation of alcohols
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The utility of 1,4-benzoquinone as a highly selective reagent for the oxidation of aryl conjugated primary allylic alcohols in the presence of benzylic and aryl conjugated secondary allylic alcohols is demonstrated. The reaction is clean, convenient and results in moderate to high yields.
- Kulkarni,Mathew
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p. 4497 - 4500
(2007/10/02)
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- Enthalpy Changes Accompanying Hydrolysis of 3-(2-Furyl)acryloylimidazole by α-Chymotrypsin
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A calorimetric analysis of the α-chymotrypsin-mediated hydrolysis of 3-(2-furyl)acryloylimidazole at pH 7.85 is presented and compared with the nonenzymatic hydrolysis.The enzyme-mediated hydrolysis is characterized by an apparent pKα for acylation of 6.60 and a deacylation pKα of 7.55.Activation enthalpy changes of 7.8+/-1.3 and 15.0+/-0.4 kcal/mol were determined for acylation (k2) and deacylation (k3), respectively.An enthalpy change of 0.04+/-0.85 kcal/mol for Michaelis complex formation was also determined from the temperature dependence of Ks.Heats of acylation (-10.1+/-0.2 kcal/mol) and deacylation (-1.2+/-0.55 kcal/mol) corrected for buffer ionization and product ionization heats were separately determined by making use of the large rate difference between acylation and deacylation (k2=1000k3) which exists at pH 7.85.The sum of these corrected enthalpy changes (-11.3+/-0.6 kcal/mol) agrees very well with the enthalpy change observed for nonenzymatic hydrolysis of furylacryloylimidazole (-11.3+/-0.5 kcal/mol) and validates the approach used.
- Slightom, J. L.,Bolen, D. W.
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p. 6318 - 6324
(2007/10/02)
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- Synthesis and Properties of 5-Bromocycloheptafuran-4-one
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5-Bromocycloheptafuran-4-one reacted with ethylamine and isopropylamine to afford the corresponding 6-amino-derivatives by a cine-substitution reaction.The behaviour of this compound towards primary amines is different from that of the non-heteroaromatic analogue 6-bromobenzocyclohepten-5-one.
- Crabbe, Pierre,Depres, Jean-Pierre
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p. 2081 - 2083
(2007/10/02)
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