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31.
Photoinduced Charge‐Transfer State of 4‐Carbazolyl‐3‐(trifluoromethyl)benzoic Acid: Photophysical Property and Application to Reduction of Carbon−Halogen Bonds as a Sensitizer 下载免费PDF全文
Prof. Dr. Ryosuke Matsubara Toshiyuki Shimada Prof. Dr. Yasuhiro Kobori Tatsushi Yabuta Prof. Dr. Toshiyuki Osakai Prof. Dr. Masahiko Hayashi 《化学:亚洲杂志》2016,11(14):2006-2010
The photoinduced persistent intramolecular charge‐transfer state of 4‐carbazolyl‐3‐(trifluoromethyl)benzoic acid was confirmed. It showed a higher catalytic activity in terms of yield and selectivity in the photochemical reduction of alkyl halides compared to the parent carbazole. Even unactivated primary alkyl bromides could be reduced by this photocatalyst. The high catalytic activity is rationalized by considering the slower backward single‐electron transfer owing to the spatial separation of the donor and acceptor subunits. 相似文献
32.
Jeon Y Sung J Kim D Seo C Cheong H Ouchi Y Ozawa R Hamaguchi HO 《The journal of physical chemistry. B》2008,112(3):923-928
Mixtures of ionic liquid (IL, 1-butyl-3-methylimidazolium tetrafluoroborate, [BMIM][BF4]) and water with varying concentrations were studied by attenuated total reflection infrared absorption and Raman spectroscopy. Changes in the peak intensities and peak positions of CHx (x = 1, 2, 3) vibration modes of the cation of the IL and OH vibration modes of the water molecules were investigated. Peaks from normal-mode stretch vibrations of CH bonds belonging to the imidazolium ring of the cation did not change their positions, while those from the terminal methyl group of the butyl chain blueshifted by approximately 10 cm-1 with the addition of water. On the other hand, change in the spectral shape in the OH stretch vibration region shows hydrogen-bonding network of water molecules breaking down rapidly as the IL is added. Trends in the change of the peak positions and the peak intensities suggested qualitative change of the intermolecular structure in the [BMIM][BF4] + H2O mixture at 32 +/- 2 and 45 +/- 2 mol/L of water concentration. 相似文献
33.
A new 20-membered macrolide designated exiguolide has been isolated from the marine sponge Geodia exigua, and its structure determined by interpretation of spectroscopic data. Exiguolide specifically inhibited fertilization of sea urchin (Hemicentrotus pulcherrimus) gametes but not embryogenesis of the fertilized egg. 相似文献
34.
Yasuda M Nakajima H Takeda R Yoshioka S Yamasaki S Chiba K Baba A 《Chemistry (Weinheim an der Bergstrasse, Germany)》2011,17(14):3856-3867
Boron complexes that contain new tridentate ligands, tris(o‐oxyaryl)methanes and ‐silanes, were prepared. These complexes had a cage‐shaped structure around a boron center and showed higher Lewis acidity and catalytic activity than open‐shaped boron compounds. The cage‐shaped ligands determined the properties of the borates by altering the geometry and were consistently bound to the metal center by chelation. The synthesized compounds were L?B(OC6H4)3CH, L?B(OC6H4)3SiMe, and its derivatives (L=THF or pyridine as an external ligand). Theoretical calculations suggested that the cage‐shaped borates had a large dihedral angle (Cipso‐O‐B‐O) compared with open‐shaped borates. The geometric effect due to the dihedral angle means that compared with open‐shaped, the cage‐shaped borates have a greater Lewis acidity. The introduction of electron‐withdrawing groups on the aryl moieties in the cage‐shaped framework increased the Lewis acidity. Substitution of a bridgehead Si for a bridgehead C decreased the Lewis acidity of the boron complexes because the large silicon atom reduces the dihedral angle of Cipso‐O‐B‐O. The ligand‐exchange rates of the para‐fluoro‐substituted compound B(OC6H3F)3CH and the ortho‐phenyl‐substituted compound B(OC6H3Ph)3CH were less than that of the unsubstituted borate B(OC6H4)3CH. The ligand‐exchange rate of B(OC6H4)3SiMe was much faster than that of B(OC6H4)3CH. A hetero Diels–Alder reaction and Mukaiyama‐type aldol reactions were more effectively catalyzed by cage‐shaped borates than by the open‐shaped borate B(OPh)3 or by the strong Lewis acid BF3?OEt2. The cage‐shaped borates with the bulky substituents at the ortho‐positions selectively catalyzed the reaction with less sterically hindered substrates, while the unsubstituted borate showed no selectivity. 相似文献
35.
Masao Tomoi Noriyuki Yanai Satoshi Shiiki Hiroshi Kakiuchi 《Journal of polymer science. Part A, Polymer chemistry》1984,22(4):911-926
Polymer-supported crown ethers were prepared from chloromethylated or ω-bromoalkylated polystyrene resins and hydroxymethylbenzo-18-crown-6 and 15- or 18-membered monoazacrown ethers. Effects of the cavity size of crown ethers, the degree of crosslinking, the degree of ring substitution, particle size, spacer chains, and solvents on the activity of the polymer-supported crown ethers in the reaction of 1-chloro- or 1-bromo-octane with aqueous NaI or KI were investigated and mechanisms of the reaction were discussed in terms of mass transfer, intraparticle diffusion, and intrinsic reactivity. 相似文献
36.
Ryosuke Sakae Dr. Koji Hirano Prof. Dr. Tetsuya Satoh Prof. Dr. Masahiro Miura 《Angewandte Chemie (International ed. in English)》2015,54(2):613-617
A copper‐catalyzed aminoboration of bicyclic alkenes, including oxa‐ and azabenzonorbornadienes, has been developed. With this method, amine and boron moieties are simultaneously introduced at an olefin with exo selectivity. Subsequent stereospecific transformations of the boryl group can provide oxygen‐ and nitrogen‐rich cyclic molecules with motifs that may be found in natural products or pharmaceutically active compounds. Moreover, a catalytic asymmetric variant of this transformation was realized by using a copper complex with a chiral bisphosphine ligand, namely (R,R)‐Ph‐BPE. 相似文献
37.
38.
Munakata R Katakai H Ueki T Kurosaka J Takao K Tadano K 《Journal of the American Chemical Society》2003,125(48):14722-14723
The first total synthesis of (+)-macquarimicin A (1), a novel inhibitor of neutral sphingomyelinase (N-SMase) with antiinflammatory activity, has been accomplished. The present work determined the absolute configuration of (+)-1 and revised the C(2)-C(3) geometry to be Z. The synthesis features a transannular Diels-Alder reaction, which constructed the tetracyclic framework stereoselectively, and a convergent and efficient synthetic pathway, which afforded (+)-macquarimicin A (1) in 27 steps (longest linear sequence) with 9.9% overall yield. 相似文献
39.
Shunsuke Murai Ryosuke Hattori Tomohiko Matoba Koji Fujita Katsuhisa Tanaka 《Journal of Non》2011,357(11-13):2259-2263
Wavelength-selective enhancement of optical birefringence has been observed in a tellurite glass containing silver nanoparticles (Ag NPs) induced via thermal poling. The birefringence appears as an optical rotation of linearly polarized light; a large optical rotation is observed at around the wavelength of localized surface plasmon resonance (LSPR) of Ag NPs. The optic axis is oriented along the electric field applied during the thermal poling, suggesting that birefringence induced in the glass matrix through the thermal poling is drastically enhanced by the NPs at around the LSPR. Because of the birefringence of the matrix, the wavelength of LSPR shifts depending on the polarization state of the incident light, which in turn induces the polarization dependence of the real part of the refractive index via the Kramers–Kronig relation. 相似文献
40.
Aunuddin Syabba Vioktalamo Ryosuke Watanabe Teruya Ishihara 《Photonics and Nanostructures》2012,10(3):325-328
Magnetic response of stratified metal dielectric metamaterial (SMDM) is demonstrated numerically and experimentally. One unit cell of SMDM has a sandwich unit cell consisting of alumina (60 nm)/silver (30 nm)/alumina (60 nm). A Mach–Zehnder interferometer is used to obtain phase information of transmittance and reflectance from which effective permeability is determined. The maximum permeability amounts to 20 and 17 for calculation and experiment, respectively. This huge resonance occurs when the magnetic field is concentrated at the metal layer, while the electric field has a node at the center. 相似文献