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81.
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83.
Yuusaku Yokoyama Masamichi Nakakoshi Hiroaki Okuno Yohko Sakamoto Satoshi Sakurai 《Magnetic resonance in chemistry : MRC》2010,48(10):811-817
The reaction mechanism for the biomimetic synthesis of tryptophan from indole and serine in the presence of Ac2O in AcOH was investigated. Although the time‐course 1H‐NMR spectra of the reaction of 5‐methoxyindole with N‐acetylserine were measured in the presence of (CD3CO)2O in CD3CO2D, the reactive intermediate could not be detected. This reaction was conducted without 5‐methoxyindole in order to elucidate the reactive intermediate, but the intermediate could not be isolated from the reaction mixture. Since the intermediate would be expected to have a very short life time, and therefore be very difficult to detect by conventional analytical methods, the structure of the intermediate was elucidated using a 2D‐NMR technique, diffusion‐ordered spectroscopy (DOSY). Two intermediates were detected and confirmed to be 2‐methyl‐4‐methyleneoxazol‐5(4H)‐one and 2‐methyl‐4‐hydroxymethyloxazol‐5(4H)‐one. The present results demonstrated that DOSY is a powerful tool for the detection of unstable intermediates. Copyright © 2010 John Wiley & Sons, Ltd. 相似文献
84.
We have developed a multifocus confocal Raman microspectroscopic system for the fast multimode vibrational imaging of living cells. It consists of an inverted microscope equipped with a microlens array, a pinhole array, a fiber bundle, and a multichannel Raman spectrometer. Forty-eight Raman spectra from 48 foci under the microscope are simultaneously obtained by using multifocus excitation and image-compression techniques. The multifocus confocal configuration suppresses the background generated from the cover glass and the cell culturing medium so that high-contrast images are obtainable with a short accumulation time. The system enables us to obtain multimode (10 different vibrational modes) vibrational images of living cells in tens of seconds with only 1 mW laser power at one focal point. This image acquisition time is more than 10 times faster than that in conventional single-focus Raman microspectroscopy. 相似文献
85.
The ring opening of alkylidenecyclopropanone acetal under acidic conditions produces the 1-alkylidene-2-oxyallyl cation as an intermediate, which reacts with furan to give the [3 + 2] and [4 + 3] cycloadducts as well as an electrophilic substitution product. The product distribution is controlled by the oxy substituents of the cation and by the solvent employed. 相似文献
86.
Tsunehisa Hirashita Shō Kuwahara Sota Okochi Makoto Tsuji Shuki Araki 《Tetrahedron letters》2010,51(14):1847-1851
In high-temperature water a series of benzyl and allylic alcohols reacted with 1,3-dicarbonyl compounds and activated aromatic compounds to give the alkylated products without added catalysts. 相似文献
87.
Haruko Ikeuchi Mitsuhiro Kanakubo Shin Okuno Rika Sato Koichi Fujita Manatsu Hamada Nobuhiro Shoda Kenta Fukui Koji Okada Hikaru Kanazawa Akira Iimori Daisaku Miyake Takeshi Takeda Gen P. Satô 《Journal of solution chemistry》2010,39(10):1428-1453
The densities and the viscosities of tris(acetylacetonato)cobalt(III) solutions in acetonitrile, dichloromethane, chloroform, tetrachloromethane, benzene, toluene, ethylbenzene, and p-xylene were measured in the dilute concentration regions at several temperatures ranging from 278 to 313 K under ambient pressure. The partial molar volumes of the solvents and solute were calculated. They are independent of concentration and increase slightly as the temperature increases. The viscosity A- and B-coefficients of the Jones-Dole equation were obtained. The A-coefficients were found to be zero within experimental error. The B-coefficients are positive and decrease as the temperature increases. Thermodynamic quantities of activation for viscous flow were calculated on the basis of Eyring’s viscosity equation. From the quantities obtained in this study, along with some information from the literature, it is suggested that structure-making interactions occur between the segments of the complex and the solvent molecules. These interactions include electrostatic interactions between the local charge on the complex and the dipole moment of the solvent in solutions of acetonitrile and dichloromethane, interlocking packing interactions along C 3-axis of the complex with solvent in solutions of chloroform and tetrachloromethane, and π-electron interactions between the chelate ring of the complex and the solvent in solutions of benzene, toluene, ethylbenzene, and p-xylene. 相似文献
88.
Hirashita T Kamei T Satake M Horie T Shimizu H Araki S 《Organic & biomolecular chemistry》2003,1(21):3799-3803
Diastereoselective couplings of salicylaldehyde, anisaldehyde and 2-pyridylaldehyde with crotyl- and cinnamylindium reagents were studied. The syl/anti selectivity was found to depend largely on the ligands on the indium atom of the allylic indium reagents. A syn-selective cinnamylation of salicylaldehyde was realized by the combination of cinnamyl acetate and indium(I) iodide, whereas an anti-selective coupling with salicylaldehyde was achieved by the indium trichloride/aluminium-mediated cinnamylation. 相似文献
89.
Background
DNA polymerase ε (Pol ε) is involved in DNA replication, repair, and cell-cycle checkpoint control in eukaryotic cells. Although the roles of replicative Pol α and Pol δ in chromosomal DNA replication are relatively well understood and well documented, the precise role of Pol ε in chromosomal DNA replication is not well understood. 相似文献90.
Murahashi T Otani T Okuno T Kurosawa H 《Angewandte Chemie (International ed. in English)》2000,39(3):537-540
The first dipalladium μ-PPh(3) complex (1) was obtained by the facile loss of two CH(3)CN ligands from [Pd(2)(PPh(3))(2)(CH(3)CN)(4)](PF(6))(2) in CH(2)Cl(2). Coupling of p-tolylacetylene (p-TolC identical withCH) with 1 or its precusor afforded the μ-butenediylidene complex 2, treatment of which with CH(3)CN resulted in PPh(3) migration to give 3. 相似文献