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101.
Shimada Y Akane H Taniguchi N Matsuhisa A Kawano N Tanaka A 《Chemical & pharmaceutical bulletin》2005,53(5):589-590
Stereoselective synthesis of methyl (Z)-(4,4-difluoro-2,3,4,5-tetrahydro-1H-1-benzazepin-5-ylidene)acetate (1a) is described. Z-selectivity of the Horner-Wadsworth-Emmons (HWE) reaction was obtained based on an investigation of the reaction conditions for introduction of a methylidene group onto the 5-position of benzazepine. 相似文献
102.
Yamagiwa N Tian J Matsunaga S Shibasaki M 《Journal of the American Chemical Society》2005,127(10):3413-3422
Full details of a catalytic asymmetric cyano-ethoxycarbonylation reaction promoted by a heterobimetallic YLi3 tris(binaphthoxide) complex (YLB 1), especially mechanistic studies, are described. In the cyanation reaction of aldehydes with ethyl cyanoformate, three achiral additives, H2O, tris(2,6-dimethoxyphenyl)phosphine oxide (3a), and BuLi, were required to achieve high reactivity and enantioselectivity (up to >99% yield and up to 98% ee). The roles of achiral additives and the reaction pathway were investigated in detail. In situ IR analysis revealed that the initiation step to generate LiCN from H2O, BuLi, and ethyl cyanoformate is rather slow. On the basis of mechanistic studies of the initiation step to generate an active nucleophilic species, reaction conditions were optimized by using a catalytic amount of acetone cyanohydrin as an initiator. Under the optimized conditions, the induction period decreased and the reaction completed within 9 min using 5 mol % YLB at -78 degrees C. Catalyst loading was successfully reduced to 1 mol %. Kinetic experiments and evaluation of the substituent effects of phosphine oxide revealed that phosphine oxide had beneficial effects on both the reaction rate and the enantioselectivity. The putative active species as well as the catalytic cycle of the reaction are also discussed. 相似文献
103.
Tomoe Sanada Kazuhiro Yamamoto Kazuo Kojima Noriyuki Wada 《Journal of Sol-Gel Science and Technology》2007,41(3):237-243
To obtain red luminants, MgO-GeO2 gel glasses and glass ceramics doped with manganese ions were prepared by a sol-gel method and their properties were investigated
by measuring X-ray diffraction (XRD), electron spin resonance (ESR), and luminescence and excitation spectra. Under UV irradiation
at 254 nm, the gel glasses and glass ceramics showed red luminescence at 620–665 nm, the intensity of which became strong
with increasing the heat-treatment temperature. A glass ceramic with the composition 1.0MnO-25MgO-75GeO2 heat treated at 1000°C exhibited the strongest red luminescence at 661 nm. From the results of XRD and ESR, this luminescence
is found to be due to the transition from the 4T1g to the 6A1g state of octahedrally coordinated Mn2+ ions located in MgGeO3 polycrystals. The luminescence wavelength of the glass ceramics (∼665 nm) is long compared with Eu3+-containing phosphors (612 nm), therefore the glass ceramics can be expected for red luminants. 相似文献
104.
Yasuda M Chiba K Ohigashi N Katoh Y Baba A 《Journal of the American Chemical Society》2003,125(24):7291-7300
Michael addition of stannyl ketone enolates to alpha,beta-unsaturated esters was accomplished in the presence of a catalytic amount of tetrabutylammonium bromide (Bu(4)NBr). Other typical systems using lithium enolate or silyl enolate with catalysts (TiCl(4) or Bu(4)NF) failed to give the desired products. The bromide anion from Bu(4)NBr coordinates to the tin center in enolate to accelerate the conjugate addition where a five-coordinated tin species was generated. The coordination of the bromide anion significantly raises the HOMO level of tin enolate and enhances its nucleophilicity. The conjugate addition provides the intermediate Michael adduct, which has an ester enolate moiety, and the adduct immediately transforms to alpha-stannyl gamma-ketoester by keto-enol tautomerization. This step contributes to the stabilization of the product system and leads to a thermodynamically favorable reaction course. An ab initio calculation reveals that the activation energy in the reaction using the bromide anion is lower than that of the reaction without using it. The transition state in either reaction course has a linear structure, not a cyclic one. This system can be applied to a variety of tin enolates and alpha,beta-unsaturated carbonyls involving enoates, enones, and unsaturated amides. 相似文献
105.
Hongbo Qin Noriyuki Yamagiwa Dr. Shigeki Matsunaga Dr. Masakatsu Shibasaki Prof. Dr. 《化学:亚洲杂志》2007,2(1):150-154
Catalytic intermolecular hydroamination of vinyl arenes is described. Our initial investigation revealed that a Bi(OTf)3/[Cu(CH3CN)4]PF6 system previously developed for catalytic intermolecular hydroamination of 1,3‐dienes was suitable for hydroamination of a styrene with sulfonamides, but the substrate generality of this system was unsatisfactory. Several metals were screened to expand the substrate scope, and a new Hf(OTf)4/[Cu(CH3CN)4]PF6 system was determined to be highly suitable. The combination of Hf(OTf)4 and [Cu(CH3CN)4]PF6 efficiently promoted the hydroamination of various vinyl arenes, including less‐reactive vinyl arenes with electron‐withdrawing groups. This strategy was applied to sulfonamides, carbamates, and carboxamides, and products were obtained in up to 99 % yield with 0.3–10 mol % catalyst loading. 相似文献
106.
Toshinobu?TokumotoEmail author Ayami?Kondo Junko?Miwa Ryo?Horiguchi Mika?Tokumoto Yoshitaka?Nagahama Noriyuki?Okida Katsutoshi?Ishikawa 《BMC biochemistry》2003,4(1):6
Background
During Xenopusoocyte maturation, the amount of a 48 kDa protein detected in the 26S proteasome fraction (p48) decreased markedly during oocyte maturation to the low levels seen in unfertilized eggs. The results indicate that the interaction of at least one protein with the 26S proteasome changes during oocyte maturation and early development. An alteration in proteasome function may be important for the regulation of developmental events, such as the rapid cell cycle, in the early embryo. In this study, we identified p48. 相似文献107.
Horikiri H Hirano N Tanaka Y Oishi J Hatakeyama H Kawamura K Nagase H 《Chemical & pharmaceutical bulletin》2004,52(6):664-669
Syntheses of 10-oxo, 10alpha-hydroxy, and 10beta-hydroxy derivatives of a potent kappa-opioid receptor selective agonist, TRK-820, are described. These derivatives were supposed to be potential degradation products in formulation of TRK-820 as a result of autoxidation. 10-Oxo-TRK-820 11 was derived from 10-oxo-4,5-epoxymorphinan 14 in 10 steps in 32% overall yield. Reduction of the 10-oxo group in 4,5-epoxymorphinan with NaBH(4) gave 10beta-hydroxy-4,5-epoxymorphinan, exclusively. A stepwise inversion method of the 10beta-hydroxy group to produce 10alpha-hydroxy-4,5-epoxymorphinan was established. By HPLC analyses, 10alpha-hydroxy-TRK-820 12 was confirmed to be one of the degradation products in developing formulation of TRK-820. 相似文献
108.
Yasumichi Matsumoto Noriyuki Tanaka Hideki Kato 《Journal of solid state chemistry》2004,177(11):4205-4212
Photoelectrochemical measurements of TiO2, NaTaO3, and Cr or Sb doped TiO2 and SrTiO3 photocatalysts were carried out in H2 and O2 saturated electrolytes in order to evaluate the reverse reactions during water photolysis. The poor activity of TiO2 as a result of reverse photoreactions of O2 reduction and H2 oxidation was revealed with the respective high cathodic and anodic photocurrents. The rise in the photocurrents at NaTaO3 after La doping was in harmony with the doping-induced increase in the photocatalytic activity. NiO loading suppresses the O2 photoreverse reactions, which declines photocatalytic activity, and/or promotes the photo-oxidation of water, because the O2 photo-reduction current was scarcely observed near the flatband potential. Photocurrents of O2 reduction and H2 oxidation were observed under visible light for the Cr and Sb doped SrTiO3 and TiO2, respectively. These phenomena are in harmony with the previous reports on the photocatalysts examined with sacrificial reagents. 相似文献
109.
We have studied oxidation reactions using a synthetic heme-thiolate (SR complex) in order to ascertain the contributions of multiple intermediates derived from heme-thiolate to the oxygen atom transfer reaction to substrate. First, degradation of peroxyphenylacetic acid (PPAA) was examined in the presence of various substrates. The O-O bond cleavage mode of PPAA was clearly dependent on the reactivity of the substrate, and an easily oxidizable substrate enhanced heterolytic O-O bond cleavage. Second, competitive oxidations of cyclooctane and cyclooctene were carried out with various peroxybenzoic acids containing a series of substituents at the para-position as an oxygen source. The ratios of alkane hydroxylation rate/alkene epoxidation rate were dependent on the nature of the para-substituent of the oxidant. We conclude that substrate and oxidant interact with each other during the oxygen atom transfer reaction, that is, oxidation reaction occurs before O-O bond cleavage, even in the reaction catalyzed by heme-thiolate, which is considered to promote O-O bond cleavage. The results of an (18)O-incorporation study that is frequently performed to determine the active intermediates derived from iron porphyrins were consistent with this conclusion. 相似文献
110.