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排序方式: 共有245条查询结果,搜索用时 15 毫秒
21.
Dr. Randa K. Gabr Prof. Dr. Takuji Hatakeyama Prof. Dr. Kazuhiro Takenaka Prof. Dr. Shinobu Takizawa Yoshihiro Okada Prof. Dr. Masaharu Nakamura Prof. Dr. Hiroaki Sasai 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(29):9518-9525
The reaction pathway of an enantioselective 5‐endo‐trig‐type cyclization of 3‐alkenoic acids catalyzed by a chiral palladium–spiro‐bis(isoxazoline) complex, Pd–SPRIX, has been studied by density functional theory calculations. The most plausible pathway involves intramolecular nucleophilic attack of the carboxylate moiety on the C?C double bond activated by Pd–SPRIX and β‐H elimination from the resulting organopalladium intermediate. The enantioselectivity was determined in the cyclization step through the formation of a π‐olefin complex, in which one of the two enantiofaces of the olefin moiety was selected. The β‐H elimination occurs via a seven‐membered cyclic structure in which the acetate ligand plays a key role in lowering the activation barrier of the transition state. In the elimination step, the SPRIX ligand was found to behave as a monodentate ligand due to the hemilability of one of the isoxazoline units thereby facilitating the elimination. Natural population analysis of this pathway showed that the more weakly electron‐donating SPRIX ligand, compared with the bis(oxazoline) ligand, BOX, facilitated the formation of the π‐olefin complex intermediate, leading to a smaller overall activation energy and a higher reactivity of the Pd–SPRIX catalyst. 相似文献
22.
Takanari Togashi Mitsuo Umetsu Takashi Naka Satoshi Ohara Yoshiharu Hatakeyama Tadafumi Adschiri 《Journal of nanoparticle research》2011,13(9):3991-3999
The assembly of metal oxide nanoparticles (NPs) on a biomolecular template by a one-pot hydrothermal synthesis method is achieved
for the first time. Magnetite (Fe3O4) nanoneedles (length: ~100 nm; width: ~10 nm) were assembled on cyclic-diphenylalanine (cFF) nanorods (length: 2–10 μm; width:
200 nm). The Fe3O4 nanoneedles and cFF nanorods were simultaneously synthesized from FeSO4 and l-phenylalanine by hydrothermal synthesis (220 °C and 22 MPa), respectively. The samples were analyzed by powder X-ray diffraction
(XRD), Fourier transform infrared spectroscopy (IR), transmission electron microscopy (TEM), and superconducting quantum interference
device (SQUID) magnetometry. Experimental results indicate that Fe3O4 nanoneedles were assembled on cFF nanorods during the hydrothermal reaction. The composite contained 3.3 wt% Fe3O4 nanoneedles without any loss of the original magnetic properties of Fe3O4. 相似文献
23.
Hironori FukumotoTomoyuki Esumi Jun IshiharaSusumi Hatakeyama 《Tetrahedron letters》2003,44(44):8047-8049
The first total synthesis of (±)-erythravine was achieved in thirteen steps from 3,4-dimethoxyphenethylamine using ring closing dienyne metathesis as the key step. 相似文献
24.
Hiroki Hirai Kiichi Nakajima Soichiro Nakatsuka Kazushi Shiren Jingping Ni Shintaro Nomura Toshiaki Ikuta Takuji Hatakeyama 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2015,127(46):13785-13789
The development of a one‐step borylation of 1,3‐diaryloxybenzenes, yielding novel boron‐containing polycyclic aromatic compounds, is reported. The resulting boron‐containing compounds possess high singlet‐triplet excitation energies as a result of localized frontier molecular orbitals induced by boron and oxygen. Using these compounds as a host material, we successfully prepared phosphorescent organic light‐emitting diodes exhibiting high efficiency and adequate lifetimes. Moreover, using the present one‐step borylation, we succeeded in the synthesis of an efficient, thermally activated delayed fluorescence emitter and boron‐fused benzo[6]helicene. 相似文献
25.
The effect of drawing on the glass-transition temperature of amorphous poly(ethylene terephthalate) has been studied. The Tg decreases to a minimum at a draw ratio of 1.5, then increases to a maximum at a draw ratio of about 2.0, and again decreases with increasing draw ratio. The relationship between the change of structure and Tg is discussed in terms of the configurational entropy and the rate of molecular motion in local-mode relaxation. On the basis of configurational entropy, the decrease of Tg at the beginning of drawing depends on the increase of configurational entropy, while at draw ratios above 2.0 it depends on the increase of entropy associated with intermolecular interaction. From the point of view of molecular motion, it is concluded that the change of Tg is determined by local oscillations in the amorphous region. 相似文献
26.
研究了蚀刻气体对生长在硅衬底上纳米晶金刚石合成的影响.合成方法为热丝化学气相沉积法,衬底温度为550 oC,反应压力为4 kPa. 其中甲烷和氢气分别作为源气体和稀释气体. 氮气、氢气和氨气用作蚀刻气体. 结果表明,仅氢气作为蚀刻气体可获得最佳工艺条件. 相似文献
27.
[Structure: see text] Beta-isocupreidine (beta-ICD)-catalyzed Baylis-Hillman reaction of chiral N-Boc-alpha-amino aldehydes and 1,1,1,3,3,3-hexafluoroisopropyl acrylate (HFIPA) takes place without racemization and exhibits the match-mismatch relationship between the substrate and the catalyst. In the case of acyclic amino aldehydes, L-substrates show excellent syn selectivity and high reactivity in contrast to D-substrates. On the other hand, in the case of cyclic amino aldehydes, D-substrates rather than L-substrates show excellent anti selectivity and high reactivity. 相似文献
28.
In the presence of 0.5-1 mol % of FeCl(3) with lithium bromide as a crucial additive, alkynyl Grignard reagents, prepared from the corresponding alkynes and methylmagnesium bromide, react with alkenyl bromides or triflates to give the corresponding conjugated enynes in high to excellent yields. The reaction shows wide applicability to various terminal alkynes and alkenyl electrophiles. 相似文献
29.
Jason E. Bara Evan S. Hatakeyama Christopher J. Gabriel Xiaohui Zeng Sonja Lessmann Douglas L. Gin Richard D. Noble 《Journal of membrane science》2008,316(1-2):186-191
Cross-linkable gemini room temperature ionic liquids (GRTILs) were synthesized and photo-cross-linked into thin films. The resultant polymer membranes were tested for their permeabilities to CO2, N2, CH4 and H2. Permeabilities for each gas were found to be much lower when compared to previously reported poly(RTIL) membranes, mainly as a result of highly restricted diffusion. Separation factors were similar to previously studied poly(RTIL) membranes. CH4 and N2 fluxes were small enough to consider these membranes as “barrier” films to the transport of those gases. Poly(GRTILs) may have use in applications where flow of those gases is not desirable. 相似文献
30.
We study a coarse-grained model of A(10)-B(20)-A(10) amphiphilic triblock copolymers in aqueous solution under confinement. We focus on the influence of the wall interaction on the morphology of the ensuing self-assembled structures. We also study the dynamics of the polymers. All our simulations are confined between two walls. We study three different combinations of walls: hydrophobic and hydrophobic, hydrophobic and hydrophilic, hydrophilic and hydrophilic. We moreover elucidate the concentration influence. The conformation and behavior of the copolymer in strongly confined systems depend on the type of wall interaction and concentration. 相似文献